Structurally-Colored Articles and Methods for Making and Using Structurally-Colored Articles

ABSTRACT

As described above, one or more aspects of the present disclosure provide articles having structural color, and methods of making articles having structural color.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to, co-pending U.S. patent applicationentitled “STRUCTURALLY-COLORED ARTICLES AND METHODS FOR MAKING AND USINGSTRUCTURALLY-COLORED ARTICLES,” filed on Jun. 26, 2019, and assignedapplication No. 62/866,778, and claims priority to, co-pending U.S.patent application entitled “STRUCTURALLY-COLORED ARTICLES AND METHODSFOR MAKING AND USING STRUCTURALLY-COLORED ARTICLES,” filed on Oct. 17,2019, and assigned application No. 62/916,292, both of which areincorporated herein by reference in their entireties.

BACKGROUND

Structural color is caused by the physical interaction of light with themicro- or nano-features of a surface and the bulk material as comparedto color derived from the presence of dyes or pigments that absorb orreflect specific wavelengths of light based on the chemical propertiesof the dyes or pigments. Color from dyes and pigments can be problematicin a number of ways. For example, dyes and pigments and their associatedchemistries for fabrication and incorporation into finished goods maynot be environmentally friendly.

BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments of the present disclosure will be more readilyappreciated upon review of the detailed description of its variousembodiments, described below, when taken in conjunction with theaccompanying drawings.

FIGS. 1A-1M shows various articles of footwear, apparel, athleticequipment, container, electronic equipment, and vision wear that includethe structure in accordance with the present disclosure, while FIGS.1N(a)-1P(b) illustrate additional details regarding different types offootwear.

FIG. 2A illustrates a side view of exemplary inorganic optical elementof the present disclosure. FIG. 2B illustrates a side view of exemplaryinorganic optical element of the present disclosure.

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

DESCRIPTION

The present disclosure provides for articles that exhibit structuralcolors through the use of an optical element having one or morereflective layers, where structural colors are visible colors produced,at least in part, through optical effects (e.g., through scattering,refraction, reflection, interference, and/or diffraction of visiblewavelengths of light), specifically a structural color (e.g., singlecolor, multicolor, iridescent). The article includes the optical element(e.g., a single layer reflector, a single layer filter, a multilayerreflector or a multilayer filter) including the reflective layer(s) andconstituent layers, where at least one reflective layer (e.g.,intermediate reflective layer) is disposed between a pair of stacks ofconstituent layers. The reflective layer has a first side and a secondside on the opposing side of the reflective layer. Each stack caninclude two or more constituent layers. A first stack is disposed on thefirst side of the reflective layer and a second stack is on the secondside of the reflective layer. The optical element can impart a firststructural color from the first side of the optical element and can alsoimpart a second structural color from the second side of the article. Inother words, each side of the optical element can present a structuralcolor, the same or different colors.

The reflective layer located between two stacks of constituent layerscan have a minimum percent reflectance, under certain conditions, ofabout 60 percent or more in the wavelength range of 380 to 740nanometers. In addition, the reflective layer can also have a maximumpercent transmittance, under certain conditions, of 30 percent or lessin the wavelength range of 380 to 740 nanometers.

The optical element can include two or more reflective layers, where oneis the intermediate reflective layer and one or more other reflectivelayers can include non-intermediate layers. The non-intermediatereflective layer can be disposed between constituent layers in one orboth of the first stack and the second stack. Two or more constituentlayers can separate the intermediate reflective layer and thenon-intermediate reflective layer. The non-intermediate reflective layergenerally has a minimum percent transmittance, under certain conditions,of about 30 percent or more.

The reflective layer (e.g., intermediate or non-intermediate reflectivelayer) can include a metal layer or an oxide layer. The oxide layer canbe a metal oxide, a doped metal oxide, or a combination thereof. Themetal layer, the metal oxide or the doped metal oxide can include thefollowing: the transition metals, the metalloids, the lanthanides, andthe actinides, as well as nitrides, oxynitrides, sulfides, sulfates,selenides, tellurides and a combination of these.

In addition, the optical element can include an optional texturedsurface, where the optical element is disposed on a surface of thearticle with the optional textured surface between the optical elementand the surface or where the textured surface is part of the opticalelement, depending upon the design. The combination of the opticalelement and the optional textured surface imparts the first structuralcolor and the second structural color, to the article, where one or bothof the first and second structural colors can be designed to bedifferent than the color of the components of the optical element and/orthe underlying material, optionally with or without the application ofpigments or dyes to the article. In this way, the structural colors canimpart an aesthetically appealing color to the article without requiringthe use of inks or pigments and the environmental impact associated withtheir use.

After disposing the optical element onto the article, the articleexhibits a different color from the underlying surface of the article,without the application of additional pigments or dyes to the article.For example, the structural color can differ from the color of theunderlying surface of the article based on a color parameter such ashue, lightness, iridescence type, or any combination thereof. Inparticular examples, the structural colors and the color of theunderlying surface of the article differ both in hue and iridescencetype, where the structural color is iridescent (e.g., exhibits two ormore different hues when viewed from at least two different angles 15degrees apart), and the color of the underlying surface is notiridescent.

The article can be a finished article such as, for example, an articleof footwear, apparel or sporting equipment. The article can be acomponent of an article of footwear, apparel or sporting equipment, suchas, for example, an upper or a sole for an article of footwear, awaistband or arm or hood of an article of apparel, a brim of a hat, aportion of a backpack, or a panel of a soccer ball, and the like. Theoptical element can be disposed on the surface so that the reflectivelayer (as well as the other layers) is parallel or substantiallyparallel the surface (e.g., the plane of the reflective layer isparallel the plane of the surface of the article) (also referred to as“in-line”, or “in-line” configuration) or so that the reflective layeris perpendicular or substantially perpendicular the surface (alsoreferred to as the optical element laying “on its side”, or “on itsside” configuration).

The optical element can be disposed (e.g., affixed, attached, adhered,bonded, joined) on a surface of one or more components of the footwear,such as on the shoe upper and/or the sole. The optical element can beincorporated into the sole by incorporating it into a cushioning elementsuch as a bladder or a foam. The sole and/or upper can be designed sothat one or more portions of the structurally colored component arevisible in the finished article, by including an opening, or atransparent component covering the structurally colored component, andthe like.

In an aspect, the optical element can be disposed on a surface of apolymeric layer of the article, where the polymeric layer has a minimumpercent transmittance of 30 percent so that the structural color fromthe side facing the polymeric layer can be observed. In this way, theoptical element can be used to provide two structural colors, one fromeach side of the optical element in the “in-line” configuration, forexample, when the optical element is disposed on the internally-facingsurface or the externally-facing surface.

The present disclosure provides for an article comprising: an opticalelement disposed on a surface of a polymeric layer of the article,wherein the polymeric layer has a minimum percent transmittance of 30percent, under a given illumination condition at a first observationangle of about −15 to 180 degrees or about −15 degrees and +60 degrees,in the wavelength range of 380 to 740 nanometers (optionally about 20percent or more, or about 15 percent or more), wherein the opticalelement has a first side and a second side opposite the first side,wherein the optical element comprises at least one reflective layer anda plurality of constituent layers, wherein the at least one reflectivelayer comprises an intermediate reflective layer that is located betweentwo constituent layers, wherein the intermediate layer has a minimumpercent reflectance, under a given illumination condition at a firstobservation angle of about −15 to 180 degrees or about −15 degrees and+60 degrees, of about 60 percent or more in the wavelength range of 380to 740 nanometers (optionally about 70 percent or more, optionally about80 percent or more, or optionally about 90 percent or more, or about 95percent or more, or about 98 percent or more) and/or a maximum percenttransmittance, under the given illumination condition at the firstobservation angle of about −15 to 180 degrees or about −15 degrees and+60 degrees, of 30 percent or less in the wavelength range of 380 to 740nanometers (optionally about 20 percent or less, about 15 percent orless, about 10 percent or less, or about 5 percent or less), wherein theoptical element imparts a first structural color to the article from thefirst side of the optical element, wherein the optical element imparts asecond structural color to the article from the second side of thearticle. The first structural color and the second structural color canbe the same or are different. Optionally, the at least one reflectivelayer includes at least one a non-intermediate reflective layer locatedbetween two constituent layers.

When measured according to the CIE 1976 color space under a givenillumination condition at a first observation angle of about −15 to 180degrees or about −15 degrees and +60 degrees, the optical element has afirst color measurement having coordinates L₁* and a₁* and b₁* asmeasured from the first side of the optical element, and optical elementhas a second color measurement having coordinates L₂* and a₂* and b₂* asmeasured from the second side of the optical element, wherein theΔE*_(ab) between the first color measurement and the second colormeasurement is greater than about 2.2, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2), or optionally theΔE*_(ab) is greater than about 3, or optionally is greater than 4, oroptionally is greater than 5. In this instance, the structural colorfrom each side are distinguishable or different.

When measured according to the CIE 1976 color space under a givenillumination condition at a first observation angle of about −15 to 180degrees or about −15 degrees and +60 degrees, the optical element has afirst color measurement having coordinates L₁* and a₁* and b₁* asmeasured from the first side of the optical element, and optical elementhas a second color measurement having coordinates L₂* and a₂* and b₂* asmeasured from the second side of the optical element, wherein theΔE*_(ab) between the first color measurement and the second colormeasurement is less than about 3, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2), or optionally theΔE*_(ab) is less than about 2.2. In this instance, the structural colorfrom each side are identical or virtually identical.

The present disclosure also provides for a method, comprising: disposingan optical element on a surface of a polymeric layer of an article,wherein the polymeric layer has a minimum percent transmittance of 30percent, wherein the optical element is described above or herein. Thepresent disclosure also provides for a product of the method asdescribed above and herein.

The present disclosure provides for a method comprising: disposing atleast two layers of a constituent layer onto a surface of a polymericlayer of an article to form a first stack, wherein the polymeric layerhas a minimum percent transmittance of 30 percent, under a givenillumination condition at a first observation angle of about −15 to 180degrees or about −15 degrees and +60 degrees, in the wavelength range of380 to 740 nanometers (optionally about 20 percent or more, or about 15percent or more); disposing an intermediate reflective layer onto thefirst stack, wherein the intermediate reflective layer has a first sidesurface adjacent the first stack and a second side surface on the sideopposite the first side surface, wherein the intermediate layer has aminimum percent reflectance, under a given illumination condition at afirst observation angle of between −15 degrees and +60 degrees, of about60 percent or more in the wavelength range of 380 to 740 nanometers(optionally about 70 percent or more, optionally about 80 percent ormore, or optionally about 90 percent or more, or about 95 percent ormore, or about 98 percent or more) and/or a maximum percenttransmittance, under the given illumination condition at the firstobservation angle of about −15 to 180 degrees or about −15 degrees and+60 degrees, of 30 percent or less in the wavelength range of 380 to 740nanometers (optionally about 20 percent or less, about 15 percent orless, about 10 percent or less, or about 5 percent or less); anddisposing at least two layers of the constituent layer onto the secondside surface of the intermediate layer to form a second stack, whereinthe first stack, the intermediate reflective layer and the second stackcomprise an optical element; and wherein the optical element imparts afirst structural color to the article from a first side of the opticalelement, wherein the optical element imparts a second structural colorto the article from a second side of the article. The present disclosurealso provides for an article comprising: a product of the method asprovided above and herein.

The present disclosure will be better understood upon reading thefollowing numbered aspects, which should not be confused with theclaims. Any of the numbered aspects below can, in some instances, becombined with aspects described elsewhere in this disclosure and suchcombinations are intended to form part of the disclosure.

Aspect 1. An article comprising:

an optical element disposed on a surface of a polymeric layer of thearticle, wherein the polymeric layer has a minimum percent transmittanceof 30 percent, under a given illumination condition at a firstobservation angle of about −15 to 180 degrees or about or about −15degrees and +60 degrees, in the wavelength range of 380 to 740nanometers (optionally about 20 percent or more, or about 15 percent ormore), wherein the optical element has a first side and a second sideopposite the first side,

wherein the optical element comprises at least one reflective layer anda plurality of constituent layers, wherein the at least one reflectivelayer comprises an intermediate reflective layer that is located betweentwo constituent layers, wherein the intermediate layer has a minimumpercent reflectance, under a given illumination condition at a firstobservation angle of about −15 to 180 degrees or about or about −15degrees and +60 degrees, of about 60 percent or more in the wavelengthrange of 380 to 740 nanometers (optionally about 70 percent or more,optionally about 80 percent or more, or optionally about 90 percent ormore, or about 95 percent or more, or about 98 percent or more) and/or amaximum percent transmittance, under the given illumination condition atthe first observation angle of about −15 to 180 degrees or about orabout −15 degrees and +60 degrees, of 30 percent or less in thewavelength range of 380 to 740 nanometers (optionally about 20 percentor less, about 15 percent or less, about 10 percent or less, or about 5percent or less), wherein the optical element imparts a first structuralcolor to the article from the first side of the optical element, whereinthe optical element imparts a second structural color to the articlefrom the second side of the article.

Aspect 2. The article of any one of the preceding aspects, wherein theintermediate reflective layer has a first side surface and a second sidesurface, wherein the second side surface is located opposite the firstside surface, wherein the first side surface of the intermediatereflective layer is on the first side of the optical element, whereinthe second side surface of the intermediate reflective layer is on thesecond side of the optical element.Aspect 3. The article of any one of the preceding aspects, wherein thefirst structural color and the second structural color are different.Aspect 4. The article of any one of the preceding aspects, wherein whenmeasured according to the CIE 1976 color space under a givenillumination condition at a first observation angle of about −15 to 180degrees or about or about −15 degrees and +60 degrees, the opticalelement has a first color measurement having coordinates L₁* and a₁* andb₁* as measured from the first side of the optical element, and opticalelement has a second color measurement having coordinates L₂* and a₂*and b₂* as measured from the second side of the optical element, whereinthe ΔE*_(ab) between the first color measurement and the second colormeasurement is greater than about 2.2, whereΔE*_(ab)=[(L₁*-L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2), or optionally theΔE*_(ab) is greater than about 3, or optionally is greater than 4, oroptionally is greater than 5, the first structural color and the secondstructural color are different.Aspect 5. The article of any one of the preceding aspects, wherein whenmeasured according to the CIE 1976 color space under a givenillumination condition at a first observation angle of about −15 to 180degrees or about or about −15 degrees and +60 degrees, the opticalelement has a first color measurement having coordinates L₁* and a₁* andb₁* as measured from the first side of the optical element, and opticalelement has a second color measurement having coordinates L₂* and a₂*and b₂* as measured from the second side of the optical element, whereinthe ΔE*_(ab) between the first color measurement and the second colormeasurement is less than about 3, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2), or optionally theΔE*_(ab) is less than about 2.2, the first structural color and thesecond structural color are the same or substantially the same.Aspect 6. The article of any one of the aspects, wherein the opticalelement is on and visible from an outside surface of the article or theoptical element is on and visible from an inside surface of the article.Aspect 7. The article of any one of the preceding aspects, wherein theoptical element is a single layer reflector, a single layer filter, amultilayer reflector or a multilayer filter.Aspect 8. The article of any one of the preceding aspects, wherein theoptical element has a first stack disposed on the first side surface ofthe intermediate reflector layer and a second stack disposed on thesecond side surface of the intermediate reflector layer, wherein thefirst stack comprises the constituent layer and the second stackincludes the constituent layers.Aspect 9. The article of any one of the preceding aspects, wherein theintermediate reflective layer is positioned at a first position in theoptical element so that light first passes through the first stack ofthe optical element prior to impinging upon the first side surface ofthe intermediate reflective layer and wherein the light first passesthrough the second stack of the optical element prior to impinging uponthe second side surface of the intermediate reflective layer.Aspect 10. The article of any one of the preceding aspects, wherein thefirst stack has 2 to 20 constituent layers and, independently, thesecond stack has 2 to 20 constituent layers, wherein, optionally, eachconstituent layer of the first stack and the second stack,independently, has a thickness of about one quarter of the wavelength ofthe wavelength to be reflected.Aspect 11. The article of any one of the preceding aspects, wherein eachof the constituent layers of the first stack have different refractiveindices, optionally wherein each constituent layer of the first stackhas a thickness of about one quarter of the wavelength of the wavelengthto be reflected; optionally wherein each of the constituent layers ofthe second stack have different refractive indices, optionally whereineach constituent layer of the second stack has a thickness of about onequarter of the wavelength of the wavelength to be reflected; optionally,wherein one or more of the constituent layers in the first stack have adifferent refractive index than one or more of the constituent layers inthe second stack; and optionally, wherein one or more of the constituentlayers in the first stack have a different thickness than one or more ofthe constituent layers in the second stack.Aspect 12. The article of any one of the preceding aspects, wherein thefirst stack and the second stack have the same order, material type, anddimensions of constituent layers from first side surface and the secondside surface of the intermediate reflective layer, respectively, so thatthe first stack and the second stack are the same.Aspect 13. The article of any one of the preceding aspects, theintermediate reflective layer has a thickness of at least 10 nanometers(optionally at least 30 nanometers, optionally at least 40 nanometers,optionally at least 50 nanometers, optionally at least 60 nanometers,optionally a thickness of from about 10 nanometers to about 100nanometers, or of from about 30 nanometers to about 80 nanometers, orfrom about 40 nanometers to about 60 nanometers).Aspect 14. The article of any one of the preceding aspects, wherein theat least one reflective layer includes at least one a non-intermediatereflective layer located between two constituent layers.Aspect 15. The article of any of one of the preceding aspects, whereinthe non-intermediate layer is not opaque.Aspect 16. The article of any of one of the preceding aspects, whereinthe non-intermediate layer has a minimum percent transmittance, underthe given illumination condition at the first observation angle of about−15 to 180 degrees or about or about −15 degrees and +60 degrees, of atleast 30 percent, or at least 25 percent, or at least 20 percent in thewavelength range of 380 to 740 nanometers.Aspect 17. The article of any of one of the preceding aspects, whereinthe first stack includes a first non-intermediate layer and optionallythe second stack includes a second non-intermediate layer.Aspect 18. The article of any one of the preceding aspects, wherein thenon-intermediate reflective layer has a thickness of less than 40nanometers (optionally less than 30 nanometers, optionally less than 20nanometers, optionally less than 10 nanometers).Aspect 19. The article of any of the preceding aspects, wherein theoptical element has a thickness of about 100 to about 700 nanometers, orof about 200 to about 500 nanometers.Aspect 20. The article of any one of the preceding aspects, wherein theat least one reflective layer is made of a material selected from ametal or a metal oxide.Aspect 21. The article of any one of the aspects, wherein the at leastone reflective layer is made of a metal.Aspect 22. The article of any one of the preceding aspects, wherein themetal is selected from the group consisting of: titanium, aluminum,silver, zirconium, chromium, magnesium, silicon, gold, platinum, and acombination thereof.Aspect 23. The article of any one of the preceding aspects, wherein theintermediate reflective layer comprises a metal selected from the groupconsisting of: titanium, aluminum, silver, zirconium, chromium,magnesium, silicon, gold, platinum, niobium, an oxide of any of these,and a combination thereof.Aspect 24. The article of any one of the preceding aspects, wherein thenon-intermediate reflective layer comprises a metal selected from thegroup consisting of: titanium, aluminum, silver, zirconium, chromium,magnesium, silicon, gold, platinum, niobium, an oxide of any of these,and a combination thereof.Aspect 25. The article of any one of the preceding aspects, wherein theconstituent layer is made of a material selected from the groupconsisting of: silicon dioxide, titanium dioxide, zinc sulphide,magnesium fluoride, tantalum pentoxide, and a combination thereof.Aspect 26. A method, comprising:

disposing an optical element on a surface of a polymeric layer of anarticle, wherein the polymeric layer has a minimum percent transmittanceof 30 percent, wherein the optical element is described in aspects 1 to25.

Aspect 27. The method of aspect 26, wherein disposing the opticalelement comprises forming the optical element on a surface of acomponent, and then disposing the component with the optical element ona surface of the article; optionally wherein the component is a film, ora textile, or a molded component.Aspect 28. The method of any one of the preceding aspects, whereinforming the optical element comprises using: physical vapor deposition,electron beam deposition, atomic layer deposition, molecular beamepitaxy, cathodic arc deposition, pulsed laser deposition, sputtering,chemical vapor deposition, plasma-enhanced chemical vapor deposition,low pressure chemical vapor deposition, wet chemistry techniques, or acombination thereof.Aspect 29. An article comprising: a product of the method of any one ofthe preceding aspects.Aspect 30. A method comprising:

disposing at least two layers of a constituent layer onto a surface of apolymeric layer of an article to form a first stack, wherein thepolymeric layer has a minimum percent transmittance of 30 percent, undera given illumination condition at a first observation angle of about −15to 180 degrees or about or about −15 degrees and +60 degrees, in thewavelength range of 380 to 740 nanometers (optionally about 20 percentor more, or about 15 percent or more);

disposing an intermediate reflective layer onto the first stack, whereinthe intermediate reflective layer has a first side surface adjacent thefirst stack and a second side surface on the side opposite the firstside surface, wherein the intermediate layer has a minimum percentreflectance, under a given illumination condition at a first observationangle of about −15 to 180 degrees or about or about −15 degrees and +60degrees, of about 60 percent or more in the wavelength range of 380 to740 nanometers (optionally about 70 percent or more, optionally about 80percent or more, or optionally about 90 percent or more, or about 95percent or more, or about 98 percent or more) and/or a maximum percenttransmittance, under the given illumination condition at the firstobservation angle of about −15 to 180 degrees or about or about-15degrees and +60 degrees, of 30 percent or less in the wavelength rangeof 380 to 740 nanometers (optionally about 20 percent or less, about 15percent or less, about 10 percent or less, or about 5 percent or less);and

disposing at least two layers of the constituent layer onto the secondside surface of the intermediate layer to form a second stack, whereinthe first stack, the intermediate reflective layer and the second stackcomprise an optical element; and

wherein the optical element imparts a first structural color to thearticle from a first side of the optical element, wherein the opticalelement imparts a second structural color to the article from a secondside of the article.

Aspect 31. The method of the preceding aspect, wherein disposing atleast two layers of the constituent layer onto the surface of thepolymeric layer of the article to form the first stack further comprisesdisposing at least one non-intermediate layer on one of the constituentlayers, wherein the non-intermediate layer is between constituentlayers.Aspect 32. The method of the preceding aspect, wherein disposing atleast two layers of the constituent layer onto the surface of thepolymeric layer of the article to form the second stack furthercomprises disposing at least one non-intermediate layer on one of theconstituent layers, wherein the non-intermediate layer is betweenconstituent layers.Aspect 33. The method of any one of the preceding aspects, whereindisposing each of the constituent layers, the intermediate reflectivelayer, the non-intermediate reflective layer, or a combination thereofcomprises using: physical vapor deposition, electron beam deposition,atomic layer deposition, molecular beam epitaxy, cathodic arcdeposition, pulsed laser deposition, sputtering, chemical vapordeposition, plasma-enhanced chemical vapor deposition, low pressurechemical vapor deposition, wet chemistry techniques, or a combinationthereof.Aspect 34. The method of any one of the preceding aspects, wherein theoptical element is described in aspects 1 to 25.Aspect 35. An article comprising: a product of the method of any one ofthe preceding aspects.Aspect 36. The methods and/or articles of any one of the precedingaspects, wherein the polymeric layer is colorless or wherein thepolymeric layer is transparent and colored.Aspect 37. The methods and/or articles of any one of the precedingaspects, wherein the polymeric layer comprises a thermoplastic material.Aspect 38. The methods and/or articles of any one of the precedingaspects, wherein the thermoplastic material includes one or morethermoplastic polyurethanes, thermoplastic polyethers, thermoplasticpolyesters, thermoplastic polyamides, thermoplastic polyolefins,thermoplastic co-polymers thereof, or a combination thereof.Aspect 39. The methods and/or articles of any one of the precedingaspects, wherein the at least one reflective layer further comprises atextured surface, and the textured surface and the optical elementimparts the first structural color, the second structural color, orboth.Aspect 40. The methods and/or articles of any one of the precedingaspects, wherein the surface of the article is a textured surface,wherein the at least one reflective layer is on the textured surface,and the textured surface of the substrate and the optical element impartthe first structural color, the second structural color, or both.Aspect 41. The methods and/or articles of any one of the precedingaspects, wherein the textured surface includes a plurality of profilefeatures and flat planar areas, wherein the profile features extendabove the flat areas of the textured surface, optionally wherein thedimensions of the profile features, a shape of the profile features, aspacing among the plurality of the profile features, in combination withthe optical element create the first structural color, the secondstructural color, or both, optionally wherein the profile features arein random positions relative to one another for a specific area,optionally wherein the spacing among the profile features is set toreduce distortion effects of the profile features from interfering withone another in regard to the first structural color, the secondstructural color, or both of the article, optionally wherein the profilefeatures and the flat areas result in at least one layer of the opticalelement having an undulating topography across the textured surface,wherein there is a planar region between neighboring profile featuresthat is planar with the flat planar areas of the textured surface,wherein the planar region has dimensions relative to the profilefeatures to impart the first structural color, the second structuralcolor, or both, optionally wherein the profile features and the flatareas result in each layer of the optical element having an undulatingtopography across the textured surface.Aspect 42. The methods and/or articles of any one of the precedingaspects, wherein the first structural color, the second structuralcolor, or both exhibits a single hue or multiple different hues whenviewed from different viewing angles at least 15 degrees apart.Aspect 43. The methods and/or articles of any one of the precedingaspects, wherein the article is a fiber.Aspect 44. The methods and/or articles of any one of the precedingaspects, wherein the article is a yarn.Aspect 45. The methods and/or articles of any one of the precedingaspects, wherein the article is a monofilament yarn.Aspect 46. The methods and/or articles of any one of the precedingaspects, wherein the article is a textile.Aspect 47. The methods and/or articles of any one of the precedingaspects, wherein the article is a knit textile.Aspect 48. The methods and/or articles of any one of the precedingaspects, wherein the article is a non-woven textile.Aspect 49. The methods and/or articles of any one of the precedingaspects, wherein the article is a non-woven synthetic leather.Aspect 50. The methods and/or articles of any one of the precedingaspects, wherein the article is a film.Aspect 51. The methods and/or articles of any one of the precedingaspects, wherein the article is an article of footwear, a component offootwear, an article of apparel, a component of apparel, an article ofsporting equipment, or a component of sporting equipment.Aspect 52. The methods and/or articles of any one of the precedingaspects, wherein the article is an article of footwear.Aspect 53. The methods and/or articles of any one of the precedingaspects, wherein the article is a sole component of an article offootwear.Aspect 54. The methods and/or articles of any one of the precedingaspects, wherein the article is foam midsole component of an article offootwear.Aspect 55. The methods and/or articles of any one of the precedingaspects, wherein the article is an upper component of an article offootwear.Aspect 56. The methods and/or articles of any one of the precedingaspects, wherein the article is a knit upper component of an article offootwear.Aspect 57. The methods and/or articles of any one of the precedingaspects, wherein the article is a non-woven synthetic leather upper foran article of footwear.Aspect 58. The methods and/or articles of any one of the precedingaspects, wherein the article is a bladder including a volume of a fluid,wherein the bladder has a first bladder wall having a first bladder wallthickness, wherein the first bladder wall has a gas transmission rate of15 cm³/m²·atm·day or less for nitrogen for an average wall thickness of20 mils.Aspect 59. The methods and/or articles of any one of the precedingaspects, wherein the article is a bladder, and the optical element isoptionally on an inside surface of the bladder or optionally the opticalelement is on an outside surface of the bladder.Aspect 60. The methods and/or articles of any preceding aspect, whereinthe first structural color, the second structural color, or both isvisible to a viewer having 20/20 visual acuity and normal color visionfrom a distance of about 1 meter from the bladder.Aspect 61. The methods and/or articles of any preceding aspect, whereinthe first structural color, the second structural color, or both have asingle hue.Aspect 62. The methods and/or articles of any preceding aspect, whereinthe first structural color, the second structural color, or bothincludes two or more hues.Aspect 63. The methods and/or articles of any preceding aspect, whereinthe first structural color, the second structural color, or both isiridescent.Aspect 64. The methods and/or articles of any preceding aspect, whereinthe first structural color, the second structural color, or both havelimited iridescence.Aspect 65. The methods and/or articles of the preceding aspect, whereinthe first structural color, the second structural color, or both havelimited iridescence such that, when each color is visible at eachpossible angle of observation is assigned to a single hue selected fromthe group consisting of the primary, secondary and tertiary colors onthe red yellow blue (RYB) color wheel, all of the assigned hues fallinto a single hue group, wherein the single hue group is one of a)green-yellow, yellow, and yellow-orange; b) yellow, yellow-orange andorange; c) yellow-orange, orange, and orange-red; d) orange-red, andred-purple; e) red, red-purple, and purple; f) red-purple, purple, andpurple-blue; g) purple, purple-blue, and blue; h) purple-blue, blue, andblue-green; i) blue, blue-green and green; and j) blue-green, green, andgreen-yellow.Aspect 66. The methods and/or articles of any one of the proceedingaspects, wherein the optical element (e.g., can be used for either thefirst structural color, second structural color, or both), as disposedonto the article, when measured according to the CIE 1976 color spaceunder a given illumination condition at three observation angles ofabout −15 to 180 degrees or about or about −15 degrees and +60 degreesand which are at least 15 degrees apart from each other, has a firstcolor measurement at a first angle of observation having coordinates L₁*and a₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, and a third colormeasurement at a third angle of observation having coordinates L₃* anda₃* and b₃*, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the a₁*, a₂*, and a₃* coordinate values may be thesame or different, wherein the b₁*, b₂*, and b₃* coordinate values maybe the same or different, and wherein the range of the combined a₁*, a₂*and a₃* values is less than about 40% of the overall scale of possiblea* values, or optionally wherein the range of the combined a₁*, a₂* anda₃* values is less than about 30% of the overall scale of possible a*values, or optionally wherein the range of the combined a₁*, a₂* and a₃*values is less than about 20% of the overall scale of possible a*values, or optionally, wherein the range of the combined a₁*, a₂* anda₃* values is less than about 10% of the overall scale of possible a*values.Aspect 67. The methods and/or articles of any one of the proceedingaspects, wherein the optical element (e.g., can be used for either thefirst structural color, second structural color, or both), as disposedonto the article, when measured according to the CIE 1976 color spaceunder a given illumination condition at three observation angles ofabout −15 to 180 degrees or about or about −15 degrees and +60 degreesand which are at least 15 degrees apart from each other, has a firstcolor measurement at a first angle of observation having coordinates L₁*and a₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, and a third colormeasurement at a third angle of observation having coordinates L₃* anda₃* and b₃*, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the a₁*, a₂*, and a₃* coordinate values may be thesame or different, wherein the b₁*, b₂*, and b₃* coordinate values maybe the same or different, and wherein the range of the combined b₁*, b₂*and b₃* values is less than about 40% of the overall scale of possibleb* values or optionally wherein the range of the combined b₁*, b₂* andb₃* values is less than about 30% of the overall scale of possible b*values, or optionally wherein the range of the combined b₁*, b₂* and b₃*values is less than about 20% of the overall scale of possible b*values, or optionally wherein the range of the combined b₁*, b₂* and b₃*values is less than about 10% of the overall scale of possible b*values.Aspect 68. The methods and/or articles of any one of the proceedingaspects, wherein the optical element (e.g., can be used for either thefirst structural color, second structural color, or both), as disposedonto to the article, when measured according to the CIE 1976 color spaceunder a given illumination condition at two observation angles of about−15 to 180 degrees or about or about −15 degrees and +60 degrees andwhich are at least 15 degrees apart from each other, has a first colormeasurement at a first angle of observation having coordinates L₁* anda₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, wherein the L₁* andL₂* values may be the same or different, wherein the a₁* and a₂*coordinate values may be the same or different, wherein the b₁* and b₂*coordinate values may be the same or different, and wherein the ΔE*_(ab)between the first color measurement and the second color measurement isgreater than or equal to about 100, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2), or optionally whereinthe ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 80, or optionally wherein theΔE*_(ab) between the first color measurement and the second colormeasurement is greater than or equal to about 3 or alternatively lessthan 3 or less than 2.2, or less than 2.Aspect 69. The methods and/or articles of any one of the proceedingaspects, wherein the optical element (e.g., can be used for either thefirst structural color, second structural color, or both), as disposedonto to the article, when measured according to the CIELCH color spaceunder a given illumination condition at three observation angles ofabout −15 to 180 degrees or about or about −15 degrees and +60 degreesand which are at least 15 degrees apart from each other, has a firstcolor measurement at a first angle of observation having coordinates L₁*and C₁* and h₁°, and a second color measurement at a second angle ofobservation having coordinates L₂* and C₂* and h₂°, and a third colormeasurement at a third angle of observation having coordinates L₃* andC₃* and h₃°, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the C₁*, C₂*, and C₃* coordinate values may be thesame or different, wherein the h₁°, h₂° and h₃° coordinate values may bethe same or different, and wherein the range of the combined h₁°, h₂°and h₃° values is greater than about 60 degrees, or optionally whereinthe range of the combined h₁°, h₂° and h₃° values is greater than about50 degrees, or optionally wherein the range of the combined h₁°, h₂° andh₃° values is greater than about 40 degrees, or optionally wherein therange of the combined h₁°, h₂° and h₃° values is greater than about 30degrees, or optionally wherein the range of the combined h₁°, h₂° andh₃° values is greater than about 20 degrees or alternatively optionallywherein the range of the combined h₁°, h₂° and h₃° values is less than10 degrees or less than 5 degrees.Aspect 70. The methods and/or articles of the preceding aspect, whereinthe reflective layer has a minimum percent reflectance of about 60percent or more (optionally about 70 percent or more, optionally about80 percent or more, or optionally about 90 percent or more, or about 95percent or more, or about 98 percent or more) for one of the followingwavelength ranges: violet 380-450 nanometer, blue 450 to 485 nanometer,cyan 485 to 500 nanometer, green 500 to 565 nanometer, yellow 564 to 590nanometer, orange 590 to 625 nanometer, red 625 to 740 nanometer;optionally wherein for the ranges not selected the minimum reflectivityis lower than that for the selected range.Aspect 71. The methods and/or articles of the preceding aspect, whereinfor the ranges not selected the minimum reflectivity is lower than thatfor the selected range by about 10 percent or more, about 20 percent ormore, about 30 percent or more, about 40 percent or more, or about 50percent or more.Aspect 72. The article and/or method of any of the preceding aspects,wherein the profile feature has at least one dimension greater than 500micrometers and optionally greater than about 600 micrometers.Aspect 73. The article and/or method of any of the preceding aspects,wherein at least one of the length and width of the profile feature isgreater than 500 micrometers or optionally both the length and the widthof the profile feature is greater than 500 micrometers.Aspect 74. The article and/or method of any of the preceding aspects,wherein the height of the profile features can be greater than 50micrometers or optionally greater than about 60 micrometers.Aspect 75. The article and/or method of any of the preceding aspects,wherein at least one of the length and width of the profile feature isless than 500 micrometers or both the length and the width of theprofile feature is less than 500 micrometers, while the height isgreater than 50 micrometers.Aspect 76. The article and/or method of any of the preceding aspects,wherein at least one of the length and width of the profile feature isgreater than 500 micrometers or both the length and the width of theprofile feature is greater than 500 micrometers, while the height isgreater than 50 micrometers.Aspect 77. The article and/or method of any of the preceding aspects,wherein at least one of the dimensions of the profile feature is in thenanometer range, while at least one other dimension is in the micrometerrange.Aspect 78. The article and/or method of any of the preceding aspects,wherein the nanometer range is about 10 nanometers to about 1000nanometers, while the micrometer range is about 5 micrometers to 500micrometers.Aspect 79 The article and/or method of any of the preceding aspects,wherein at least one of the length and width of the profile feature isin the nanometer range, while the other of the length and the width ofthe profile feature is in the micrometer range.Aspect 80. The article and/or method of any of the preceding aspects,wherein height of the profile features is greater than 250 nanometers.Aspect 81. The article and/or method of any of the preceding aspects,wherein at least one of the length and width of the profile feature isin the nanometer range and the other in the micrometer range, where theheight is greater than 250 nanometers.Aspect 82. The article and/or method of any of the preceding aspects,wherein spatial orientation of the profile features is periodic.Aspect 83. The article and/or method of any of the preceding aspects,wherein spatial orientation of the profile features is a semi-randompattern or a set pattern.Aspect 84. The article and/or method of any of the preceding aspects,wherein the surface of the layers of the inorganic optical element are asubstantially three-dimensional flat planar surface or athree-dimensional flat planar surface.

Now having described embodiments of the present disclosure generally,additional discussion regarding embodiments will be described in greaterdetails.

This disclosure is not limited to particular embodiments described, andas such may, of course, vary. The terminology used herein serves thepurpose of describing particular embodiments only, and is not intendedto be limiting, since the scope of the present disclosure will belimited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

The present disclosure provides for articles that exhibit structuralcolor (e.g., structurally color articles). An optical element (e.g., asingle layer reflector, a single layer filter, a multilayer reflector ora multilayer filter) disposed on the article can provide structuralcolor(s) from a first side and a second side of the optical element,where the structural color on each side are the same or different. Thestructural color is visible color produced, at least in part, throughoptical effects such as through scattering, refraction, reflection,interference, and/or diffraction of visible wavelengths of light. Thestructural color from the first side and second side can be a singlecolor, multicolor, or iridescent. In this way, articles including theoptical element can provide for appealing visual colors from each sideof the optical element.

The optical element can include a first stack and a second stack, wherea reflective layer (e.g., intermediate reflective layer) is between thefirst and second stack. Each of the first stack and the second stack cancomprise two or more constituent layers and optionally one or moreadditional reflective layers (e.g., non-intermediate reflective layers).In other words, the optical element can have the followingconfiguration: first stack/reflective layer/second stack, where one orboth of the first stack and the second stack can have the followingconfiguration: “n” constituent layers/optional non-intermediatereflective layer/“m” constituent layers (n and m can independently be 1to 30 or more). Also as described herein, the optical element canoptionally include the textured surface, such as a texture layer and/ora textured structure. Additionally and optionally, the optical elementcan include one or more layers (e.g., protection layer, and the like).The optical element can be incorporated onto one or more components ofthe article, for example, when the article is an article of footwear, onan upper or sole of an article of footwear.

The reflective layer can be an intermediate reflective layer or anon-intermediate reflective layer. The intermediate reflective layer islocated between two stacks of constituent layers, while thenon-intermediate reflective layer can be within one or both of the firststack and second stack. The intermediate reflective layer can have aminimum percent reflectance, under certain conditions, of about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 95 percent or more, in the wavelengthrange of 380 to 740 nanometers. In addition, the intermediate reflectivelayer can also have a maximum percent transmittance, under certainconditions, of about 30 percent or less, about 20 percent or less, about10 percent or less, about 5 percent or less, in the wavelength range of380 to 740 nanometers. The non-intermediate reflective layer can alsohave a minimum percent transmittance, under certain conditions, of about30 percent or more, about 20 percent or more, about 10 percent or more,about 5 percent or more, in the wavelength range of 380 to 740nanometers. The conditions for each comprise the reflective layer (e.g.,intermediate and non-intermediate reflective layers) under a givenillumination condition at a first observation angle of about −15 to 180degrees or about −15 degrees and +60 degrees. The illumination conditioncan be a wide variety of conditions such as natural illumination (e.g.,daylight, dawn, dusk), manmade illumination such as outdoor (e.g.,street lights, automobile head lights, and the like), indoor (e.g.,indoor lighting), or a combination of natural illumination and manmadeillumination, indoor or outdoor.

A minimum percent transmittance of greater than 50 percent is an opaquelayer, a minimum percent transmittance of 20 to 50 percent to besemi-transparent, and a minimum percent transmittance of less than 20percent is transparent.

The optical element can be disposed on a surface in a variety of ways.For example, the optical element can be disposed on the surface so thateach of the layers of the optical element are parallel or substantiallyparallel the surface (e.g., disposed “in line”). In other words, thelength and width of the layers of the optical element define the plane,while the thickness of the layer is the smallest dimension. In thisregard, the first side of the optical layer could be disposed on asurface that is not opaque so that light can pass through the surface tothe optical element. As a result, the light passing through the surfaceirradiating the first side of the optical element can result in thefirst structural color while light irradiating the second side of theoptical element can result in the second structural color. In an aspect,the surface can be a polymeric layer that is not opaque. The polymericlayer can be transparent or semi-transparent. The polymeric layer canhave a minimum percent transmittance of about 30 percent or more, about20 percent or more, or about 15 percent or more. In other words, enoughlight can pass through the polymeric layer under lighting conditions(e.g., day light, dusk, indoor living lighting conditions, and the like)to generate the first structural color. The polymeric layer can includeone or more polymers selected from the group consisting of polyesters,polyethers, polyamides, polyurethanes, polyolefins copolymers of each,and combinations thereof.

In another example, each of the layers of the optical element areperpendicular or substantially perpendicular the surface. In otherwords, the optical element can be considered as laying “on its side” onthe surface. In this way, light irradiating the first side of theoptical element generates the first structural color on the first sideof the optical element while light irradiating the second side of theoptical element generates the second structural color on the second sideof the optical element. In either configuration, the optical element canproduce an aesthetically pleasing appearance.

In one or more embodiments of the present disclosure the surface of thearticle includes the optical element, and is optionally a texturedsurface, where the optical element and optionally the textured surfaceimpart structural color (e.g., single color, multicolor, iridescent).The optional textured surface can be disposed between the opticalelement and the surface or be part of the optical element, dependingupon the design.

Having described the present disclosure generally, additional detailsare provided. The optical element can include the intermediatereflective layer between the first stack and the second stack. Theintermediate reflective layer can have a thickness of at least 10nanometers, optionally at least 30 nanometers, at least 40 nanometers,at least 50 nanometers, at least 60 nanometers, at least 100 nanometers,at least 150 nanometers, optionally a thickness of from about 10nanometers to about 250 nanometers or more, about 10 nanometers to about200 nanometers, about 10 nanometers to about 150 nanometers, about 10nanometers to about 100 nanometers, or of from about 30 nanometers toabout 80 nanometers, or from about 40 nanometers to about 60 nanometers.For example, the intermediate reflective layer can be about 30 to 150nanometers thick.

The optical element can include one or more non-intermediate reflectivelayers. The non-intermediate reflective layer(s) can be present in oneor both of the first stack and the second stack. The non-intermediatereflective layer can have a thickness of less than 40 nanometers,optionally less than 30 nanometers, optionally less than 20 nanometers,optionally less than 10 nanometers. For example, the non-intermediatelayer can be 20 to 30 nanometers thick. The non-intermediate reflectivelayer is not opaque.

The reflective layer (e.g., intermediate or non-intermediate reflectivelayer) can include a metal layer or an oxide layer. The oxide layer canbe a metal oxide, a doped metal oxide, or a combination thereof. Themetal layer, the metal oxide or the doped metal oxide can include thefollowing: the transition metals, the metalloids, the lanthanides, andthe actinides, as well as nitrides, oxynitrides, sulfides, sulfates,selenides, tellurides and a combination of these. The metal layer can betitanium, aluminum, silver, zirconium, chromium, magnesium, silicon,gold, platinum, and a combination thereof. The metal oxide can includetitanium oxide, silver oxide, aluminum oxide, silicon dioxide, tindioxide, chromia, iron oxide, nickel oxide, silver oxide, cobalt oxide,zinc oxide, platinum oxide, palladium oxide, vanadium oxide, molybdenumoxide, lead oxide, and combinations thereof as well as doped versions ofeach. In some aspects, the reflective layer can consist essentially of ametal oxide. In some aspects, the reflective layer can consistessentially of titanium dioxide. The metal oxide can be doped withwater, inert gasses (e.g., argon), reactive gasses (e.g., oxygen ornitrogen), metals, small molecules, and a combination thereof. In someaspects, the reflective layer can consist essentially of a doped metaloxide or a doped metal oxynitride or both. In an aspect, the reflectivelayer can be made of Ti or TiTiO_(x) (x=1-2). The density of the Tilayer or TiO_(x) layer can be about 3 to 6 grams per centimeter cubed,about 3 to 5 grams per centimeter cubed, about 4 to 5 grams percentimeter cubed, or 4.5 grams per centimeter cubed.

The material of the metal layer can be selected based on the desiredstructural color to be produced. Select materials reflect somewavelengths more than other wavelengths. In this way, the material ofthe reflective layer can be selected based on the desired structuralcolor. The optical element (e.g., intermediate and/or non-intermediatereflective layer) including the reflective layer can have a minimumpercent reflectance for one or more of the following wavelength ranges:violet 380 to 450 nanometer, blue 450 to 485 nanometer, cyan 485 to 500nanometer, green 500 to 565 nanometer, yellow 564 to 590 nanometer,orange 590 to 625 nanometer, or red 625 to 740 nanometer. The reflectivelayer can have a minimum percent reflectance for one or more wavelengthwidths (e.g., about 10 nanometers, about 20 nanometers, about 30nanometers, about 40 nanometers, about 50 nanometers, about 60nanometers, about 75 nanometers, or about 100 nanometers) in the rangefrom 380 to 740 nanometers. For the ranges not selected in a particularconfiguration, the minimum reflectivity is lower than that for theselected range, for example, the minimum reflectivity is lower than thatfor the selected range by about 10 percent or more, about 20 percent ormore, about 30 percent or more, about 40 percent or more, or about 50percent or more. In an aspect, the reflective layer can be Al orAlO_(x), where the structural color is iridescent. In another example,the reflective layer can Ti or TiO_(x), where the structural color canbe one or more hues of blue or one or more hues of green, or acombination thereof.

The reflective layer (e.g., intermediate reflective layer) can be acoating on the surface of the article. The coating can be chemicallybonded (e.g., covalently bonded, ionically bonded, hydrogen bonded, andthe like) to the surface of the article. The coating has been found tobond well to a surface made of a polymeric material. In an example, thesurface of the article can be made of a polymeric material such as apolyurethane, including a thermoplastic polyurethane (TPU), as thosedescribed herein. Additional details about the optical element and thereflective layer(s) are provided herein.

In an embodiment, the structural color is not used in combination with apigment and/or dye. In another aspect, the structural color is used incombination with a pigment and/or dye, but the structural color is notthe same color, shade, and/or hue as the pigment and/or dye. In thisregard, the structural color is the product of the textured surface, theoptical element, and the pigment and/or dye.

In an embodiment, the structural color is used in combination with apigment and/or dye to enhance the color of the pigment and/or dye inregard to the color of the pigment and/or dye or enhance a tone, tint,shade, or hue associated with the pigment and/or dye.

The article can be an article of manufacture or a component of thearticle. The article of manufacture can include footwear, apparel (e.g.,shirts, jerseys, pants, shorts, gloves, glasses, socks, hats, caps,jackets, undergarments), containers (e.g., backpacks, bags), andupholstery for furniture (e.g., chairs, couches, car seats), bedcoverings (e.g., sheets, blankets), table coverings, towels, flags,tents, sails, and parachutes, or components of any one of these. Inaddition, the optical element can be used with or disposed on textilesor other items such as striking devices (e.g., bats, rackets, sticks,mallets, golf clubs, paddles, etc.), athletic equipment (e.g., golfbags, baseball and football gloves, soccer ball restriction structures),protective equipment (e.g., pads, helmets, guards, visors, masks,goggles, etc.), locomotive equipment (e.g., bicycles, motorcycles,skateboards, cars, trucks, boats, surfboards, skis, snowboards, etc.),balls or pucks for use in various sports, fishing or hunting equipment,furniture, electronic equipment, construction materials, eyewear,timepieces, jewelry, and the like.

The article can be an article of footwear. The article of footwear canbe designed for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. Primarily, the article offootwear is intended for outdoor use on unpaved surfaces (in part or inwhole), such as on a ground surface including one or more of grass,turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether asan athletic performance surface or as a general outdoor surface.However, the article of footwear may also be desirable for indoorapplications, such as indoor sports including dirt playing surfaces forexample (e.g., indoor baseball fields with dirt infields).

In particular, the article of footwear can be designed for use in indooror outdoor sporting activities, such as global football/soccer, golf,American football, rugby, baseball, running, track and field, cycling(e.g., road cycling and mountain biking), and the like. The article offootwear can optionally include traction elements (e.g., lugs, cleats,studs, and spikes as well as tread patterns) to provide traction on softand slippery surfaces, where components of the present disclosure can beused or applied between or among the traction elements and optionally onthe sides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

In particular, the article can be an article of apparel (i.e., agarment). The article of apparel can be an article of apparel designedfor athletic or leisure activities. The article of apparel can be anarticle of apparel designed to provide protection from the elements(e.g., wind and/or rain), or from impacts.

In particular, the article can be an article of sporting equipment. Thearticle of sporting equipment can be designed for use in indoor oroutdoor sporting activities, such as global football/soccer, golf,American football, rugby, baseball, running, track and field, cycling(e.g., road cycling and mountain biking), and the like.

FIGS. 1A-1M illustrates footwear, apparel, athletic equipment,container, electronic equipment, and vision wear that include thestructure (e.g., the optical element, optionally the textured surface)of the present disclosure. The structure can include the optical elementin the “in-line” configuration and/or the “on its side” configuration.The structure including the optical element is represented by hashedareas 12A′/12M′-12A″/12M′. The location of the structure is providedonly to indicate one possible area that the structure can be located.Also, two locations are illustrated in some of the figures and onelocation is illustrated in other figures, but this is done only forillustration purposes as the items can include one or a plurality ofstructure, where the size and location can be determined based on theitem. The structure(s) located on each item can represent a number,letter, symbol, design, emblem, graphic mark, icon, logo, or the like.

FIGS. 1N(a) and 1N(b) illustrate a perspective view and a side view ofan article of footwear 100 that include a sole structure 104 and anupper 102. The structure including the inorganic optical element isrepresented by 122 a and 122 b. The sole structure 104 is secured to theupper 102 and extends between the foot and the ground when the articleof footwear 100 is worn. The primary elements of the sole structure 104are a midsole 114 and an outsole 112. The midsole 114 is secured to alower area of the upper 102 and may be formed of a polymer foam oranother appropriate material. In other configurations, the midsole 114can incorporate fluid-filled chambers, plates, moderators, and/or otherelements that further attenuate forces, enhance stability, or influencemotions of the foot. The outsole 112 is secured to a lower surface ofthe midsole 114 and may be formed from a wear-resistant rubber materialthat is textured to impart traction, for example. The upper 102 can beformed from various elements (e.g. lace, tongue, collar) that combine toprovide a structure for securely and comfortably receiving a foot.Although the configuration of the upper 102 may vary significantly, thevarious elements generally define a void within the upper 102 forreceiving and securing the foot relative to sole structure 104. Surfacesof the void within upper 102 are shaped to accommodate the foot and canextend over the instep and toe areas of the foot, along the medial andlateral sides of the foot, under the foot, and around the heel area ofthe foot. The upper 102 can be made of one or more materials such astextiles, a polymer foam, leather, synthetic leather, and the like thatare stitched or bonded together. Although this configuration for thesole structure 104 and the upper 102 provides an example of a solestructure that may be used in connection with an upper, a variety ofother conventional or nonconventional configurations for the solestructure 104 and/or the upper 102 can also be utilized. Accordingly,the configuration and features of the sole structure 104 and/or theupper 102 can vary considerably.

FIGS. 1O(a) and 1O(b) illustrate a perspective view and a side view ofan article of footwear 130 that include a sole structure 134 and anupper 132. The structure including the inorganic optical element isrepresented by 136 a and 136 b/136 b′. The sole structure 134 is securedto the upper 132 and extends between the foot and the ground when thearticle of footwear 130 is worn. The upper 132 can be formed fromvarious elements (e.g., lace, tongue, collar) that combine to provide astructure for securely and comfortably receiving a foot. Although theconfiguration of the upper 132 may vary significantly, the variouselements generally define a void within the upper 132 for receiving andsecuring the foot relative to the sole structure 134. Surfaces of thevoid within the upper 132 are shaped to accommodate the foot and canextend over the instep and toe areas of the foot, along the medial andlateral sides of the foot, under the foot, and around the heel area ofthe foot. The upper 132 can be made of one or more materials such astextiles including natural and synthetic leathers, molded polymericcomponents, polymer foam and the like that are stitched or bondedtogether.

The primary elements of the sole structure 134 are a forefoot component142, a heel component 144, and an outsole 146. Each of the forefootcomponent 142 and the heel component 144 are directly or indirectlysecured to a lower area of the upper 132 and formed from a polymermaterial that encloses a fluid, which may be a gas, liquid, or gel.During walking and running, for example, the forefoot component 142 andthe heel component 144 compress between the foot and the ground, therebyattenuating ground reaction forces. That is, the forefoot component 142and the heel component 144 are inflated and may be pressurized with thefluid to cushion the foot. The outsole 146 is secured to lower areas ofthe forefoot component 142 and the heel component 144 and may be formedfrom a wear-resistant rubber material that is textured to imparttraction. The forefoot component 142 can be made of one or more polymers(e.g. layers of one or more polymers films) that form a plurality ofchambers that includes a fluid such as a gas. The plurality of chamberscan be independent or fluidically interconnected. Similarly, the heelcomponent 144 can be made of one or more polymers (e.g., layers of oneor more polymers films) that form a plurality of chambers that includesa fluid such as a gas and can also be independent or fluidicallyinterconnected. In some configurations, the sole structure 134 mayinclude a foam layer, for example, that extends between the upper 132and one or both of the forefoot component 142 and the heel component144, or a foam element may be located within indentations in the lowerareas of the forefoot component 142 and the heel component 144. In otherconfigurations, the sole structure 132 may incorporate plates,moderators, lasting elements, or motion control members that furtherattenuate forces, enhance stability, or influence the motions of thefoot, for example. Although the depicted configuration for the solestructure 134 and the upper 132 provides an example of a sole structurethat may be used in connection with an upper, a variety of otherconventional or nonconventional configurations for the sole structure134 and/or the upper 132 can also be utilized. Accordingly, theconfiguration and features of the sole structure 134 and/or the upper132 can vary considerably.

FIG. 1O(c) is a cross-sectional view of A-A that depicts the upper 132and the heel component 144. The optical element 136 b can be disposed onthe outside wall of the heel component 144 or alternatively oroptionally the optical element 136 b′ can be disposed on the inside wallof the heel component 144.

FIGS. 1P(a) and 1P(b) illustrate a perspective view and a side view ofan article of footwear 160 that includes traction elements 168. Thestructure including the inorganic optical element is represented by 172a and 172 b, The article of footwear 160 includes an upper 162 and asole structure 164, where the upper 162 is secured to the sole structure164. The sole structure 164 can include one or more of a toe plate 166a, a mid-plate 166 b, and a heel plate 166 c. The plate can include oneor more traction elements 168, or the traction elements can be applieddirectly to a ground-facing surface of the article of footwear.

As shown in FIGS. 1P(a) and (b), the traction elements 168 are cleats,but the traction elements can include lugs, cleats, studs, and spikes aswell as tread patterns to provide traction on soft and slipperysurfaces. In general, the cleats, studs and spikes are commonly includedin footwear designed for use in sports such as global football/soccer,golf, American football, rugby, baseball, and the like, while lugsand/or exaggerated tread patterns are commonly included in footwear (notshown) including boots design for use under rugged outdoor conditions,such as trail running, hiking, and military use. The sole structure 164is secured to the upper 162 and extends between the foot and the groundwhen the article of footwear 160 is worn. The upper 162 can be formedfrom various elements (e.g., lace, tongue, collar) that combine toprovide a structure for securely and comfortably receiving a foot.Although the configuration of the upper 162 may vary significantly, thevarious elements generally define a void within the upper 162 forreceiving and securing the foot relative to the sole structure 164.Surfaces of the void within upper 162 are shaped to accommodate the footand extend over the instep and toe areas of the foot, along the medialand lateral sides of the foot, under the foot, and around the heel areaof the foot. The upper 162 can be made of one or more materials such astextiles including natural and synthetic leathers, molded polymericcomponents, a polymer foam, and the like that are stitched or bondedtogether. In other aspects not depicted, the sole structure 164 mayincorporate foam, one or more fluid-filled chambers, plates, moderators,or other elements that further attenuate forces, enhance stability, orinfluence the motions of the foot. Although the depicted configurationfor the sole structure 164 and the upper 162 provides an example of asole structure that may be used in connection with an upper, a varietyof other conventional or nonconventional configurations for the solestructure 164 and/or the upper 162 can also be utilized. Accordingly,the configuration and features of the sole structure 164 and/or theupper 162 can vary considerably.

As has been described herein, the structural color (e.g., the firststructural color and the second structural color) can include one of anumber of colors. The “color” of the article as perceived by a viewercan differ from the actual color of the article, as the color perceivedby a viewer is determined by the actual color of the article by thepresence of optical elements which may absorb, refract, interfere with,or otherwise alter light reflected by the article, by the viewer'sability to detect the wavelengths of light reflected by the article, bythe wavelengths of light used to illuminate the article, as well asother factors such as the coloration of the environment of the article,and the type of incident light (e.g., sunlight, fluorescent light, andthe like). As a result, the color of an object as perceived by a viewercan differ from the actual color of the article.

Conventionally, color is imparted to man-made objects by applyingcolored pigments or dyes to the object. More recently, methods ofimparting “structural color” to man-made objects have been developed.Structural color is color which is produced, at least in part, bymicroscopically structured surfaces that interfere with visible lightcontacting the surface.

The structural color is color caused by physical phenomena including thescattering, refraction, reflection, interference, and/or diffraction oflight, unlike color caused by the absorption or emission of visiblelight through coloring matters. For example, optical phenomena whichimpart structural color can include multilayer interference, thin-filminterference, refraction, dispersion, light scattering, Mie scattering,diffraction, and diffraction grating. In various aspects describedherein, structural color imparted to an article can be visible to aviewer having 20/20 visual acuity and normal color vision from adistance of about 1 meter from the article.

As described herein, structural color is produced, at least in part, bythe optical element, as opposed to the color being produced solely bypigments and/or dyes. The coloration of a structurally-colored articlecan be due solely to structural color (i.e., the article, a coloredportion of the article, or a colored outer layer of the article can besubstantially free of pigments and/or dyes). Structural color can alsobe used in combination with pigments and/or dyes, for example, to alterall or a portion of a structural color.

“Hue” is commonly used to describe the property of color which isdiscernible based on a dominant wavelength of visible light, and isoften described using terms such as magenta, red, orange, yellow, green,cyan, blue, indigo, violet, etc. or can be described in relation (e.g.,as similar or dissimilar) to one of these. The hue of a color isgenerally considered to be independent of the intensity or lightness ofthe color. For example, in the Munsell color system, the properties ofcolor include hue, value (lightness) and chroma (color purity).Particular hues are commonly associated with particular ranges ofwavelengths in the visible spectrum: wavelengths in the range of about700 to 635 nanometers are associated with red, the range of about 635 to590 nanometers is associated with orange, the range of about 590 to 560nanometers is associated with yellow, the range of about 560 to 520nanometers is associated with green, the range of about 520 to 490nanometers is associated with cyan, the range of about 490 nanometers to450 nanometers is associated with blue, and the range of about 450 to400 nanometers is associated with violet.

The color (including the hue) of an article as perceived by a viewer candiffer from the actual color of the article. The color as perceived by aviewer depends not only on the physics of the article, but also itsenvironment, and the characteristics of the perceiving eye and brain.For example, as the color perceived by a viewer is determined by theactual color of the article (e.g., the color of the light leaving thesurface of the article), by the viewer's ability to detect thewavelengths of light reflected or emitted by the article, by thewavelengths of light used to illuminate the article, as well as otherfactors such as the coloration of the environment of the article, andthe type of incident light (e.g., sunlight, fluorescent light, and thelike). As a result, the color of an object as perceived by a viewer candiffer from the actual color of the article.

When used in the context of structural color (e.g., first and/or secondstructural color), one can characterize the hue of astructurally-colored article, i.e., an article that has beenstructurally colored by incorporating an optical element into thearticle, based on the wavelengths of light the structurally-coloredportion of the article absorbs and reflects (e.g., linearly andnon-linearly). While the optical element may impart a first structuralcolor, the presence of an optional textured surface can alter thestructural color. Other factors such as coatings or transparent elementsmay further alter the perceived structural color. The hue of thestructurally colored article can include any of the hues describedherein as well as any other hues or combination of hues. The structuralcolor can be referred to as a “single hue” (i.e., the hue remainssubstantially the same, regardless of the angle of observation and/orillumination), or “multihued” (i.e., the hue varies depending upon theangle of observation and/or illumination). The multihued structuralcolor can be iridescent (i.e., the hue changes gradually over two ormore hues as the angle of observation or illumination changes). The hueof an iridescent multihued structural color can change gradually acrossall the hues in the visible spectrum (e.g., like a “rainbow”) as theangle of observation or illumination changes. The hue of an iridescentmultihued structural color can change gradually across a limited numberof hues in the visible spectrum as the angle of observation orillumination changes, in other words, one or more hues in the visiblespectrum (e.g., red, orange, yellow, etc.) are not observed in thestructural color as the angle of observation or illumination changes.Only one hue, or substantially one hue, in the visible spectrum may bepresent for a single-hued structural color. The hue of a multihuedstructural color can change more abruptly between a limited number ofhues (e.g., between 2-8 hues, or between 2-4 hues, or between 2 hues) asthe angle of observation or illumination changes.

The structural color can be a multi-hued structural color in which twoor more hues are imparted by the structural color.

The structural color can be iridescent multi-hued structural color inwhich the hue of the structural color varies over a wide number of hues(e.g., 4, 5, 6, 7, 8 or more hues) when viewed at a single viewingangle, or when viewed from two or more different viewing angles that areat least 15 degrees apart from each other.

The structural color can be limited iridescent multi-hue structuralcolor in which the hue of the structural color varies, or variessubstantially (e.g., about 90 percent, about 95 percent, or about 99percent) over a limited number of hues (e.g., 2 hues, or 3 hues) whenviewed from two or more different viewing angles that are at least 15degrees apart from each other. In some aspects, a structural colorhaving limited iridescence is limited to two, three or four huesselected from the RYB primary colors of red, yellow and blue, optionallythe RYB primary and secondary colors of red, yellow, blue, green, orangeand purple, or optionally the RYB primary, secondary and tertiary colorsof red, yellow, blue, green, orange purple, green-yellow, yellow-orange,orange-red, red-purple, purple-blue, and blue-green.

The structural color can be single-hue angle-independent structuralcolor in which the hue, the hue and value, or the hue, value and chromaof the structural color is independent of or substantially (e.g., about90 percent, about 95 percent, or about 99 percent) independent of theangle of observation. For example, the single-hue angle-independentstructural color can display the same hue or substantially the same huewhen viewed from at least 3 different angles that are at least 15degrees apart from each other (e.g., single-hue structural color).

The structural color imparted can be a structural color having limitediridescence such that, when each color observed at each possible angleof observation is assigned to a single hue selected from the groupconsisting of the primary, secondary and tertiary colors on the redyellow blue (RYB) color wheel, for a single structural color, all of theassigned hues fall into a single hue group, wherein the single hue groupis one of a) green-yellow, yellow, and yellow-orange; b) yellow,yellow-orange and orange; c) yellow-orange, orange, and orange-red; d)orange-red, and red-purple; e) red, red-purple, and purple; f)red-purple, purple, and purple-blue; g) purple, purple-blue, and blue;h) purple-blue, blue, and blue-green; i) blue, blue-green and green; andj) blue-green, green, and green-yellow. In other words, in this exampleof limited iridescence, the hue (or the hue and the value, or the hue,value and chroma) imparted by the structural color varies depending uponthe angle at which the structural color is observed, but the hues ofeach of the different colors viewed at the various angles ofobservations varies over a limited number of possible hues. The huevisible at each angle of observation can be assigned to a singleprimary, secondary or tertiary hue on the red yellow blue (RYB) colorwheel (i.e., the group of hues consisting of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green). For example, while a plurality ofdifferent colors are observed as the angle of observation is shifted,when each observed hue is classified as one of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green, the list of assigned hues includes no morethan one, two, or three hues selected from the list of RYB primary,secondary and tertiary hues. In some examples of limited iridescence,all of the assigned hues fall into a single hue group selected from huegroups a)-j), each of which include three adjacent hues on the RYBprimary, secondary and tertiary color wheel. For example, all of theassigned hues can be a single hue within hue group h) (e.g., blue), orsome of the assigned hues can represent two hues in hue group h) (e.g.,purple-blue and blue), or can represent three hues in hue group h)(e.g., purple-blue, blue, and blue-green).

Similarly, other properties of the structural color, such as thelightness of the color, the saturation of the color, and the purity ofthe color, among others, can be substantially the same regardless of theangle of observation or illumination, or can vary depending upon theangle of observation or illumination. The structural color can have amatte appearance, a glossy appearance, or a metallic appearance, or acombination thereof.

As discussed above, the color (including hue) of a structurally-coloredarticle (e.g., an article include structural color) can vary dependingupon the angle at which the structurally-colored article is observed orilluminated. The hue or hues of an article can be determined byobserving the article, or illuminating the article, at a variety ofangles using constant lighting conditions. As used herein, the “angle”of illumination or viewing is the angle measured from an axis or planethat is orthogonal to the surface. The viewing or illuminating anglescan be set between about 0 and 180 degrees. The viewing or illuminatingangles can be set at 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60degrees, and −15 degrees and the color can be measured using acolorimeter or spectrophotometer (e.g., Konica Minolta), which focuseson a particular area of the article to measure the color. The viewing orilluminating angles can be set at 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, 75 degrees, 90 degrees, 105 degrees, 120 degrees,135 degrees, 150 degrees, 165 degrees, 180 degrees, 195 degrees, 210degrees, 225 degrees, 240 degrees, 255 degrees, 270 degrees, 285degrees, 300 degrees, 315 degrees, 330 degrees, and 345 degrees and thecolor can be measured using a colorimeter or spectrophotometer. In aparticular example of a multihued article colored using only structuralcolor, when measured at 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees, the hues measured for article consisted of“blue” at three of the measurement angles, “blue-green” at 2 of themeasurement angles and “purple” at one of the measurement angles.

In other embodiments, the color (including hue, value and/or chroma) ofa structurally-colored article does not change substantially, if at all,depending upon the angle at which the article is observed orilluminated. In instances such as this the structural color can be anangle-independent structural color in that the hue, the hue and value,or the hue, value and chroma observed is substantially independent or isindependent of the angle of observation.

Various methodologies for defining color coordinate systems exist. Oneexample is L*a*b* color space, where, for a given illuminationcondition, L* is a value for lightness, and a* and b* are values forcolor-opponent dimensions based on the CIE coordinates (CIE 1976 colorspace or CIELAB). In an embodiment, an article having structural color(e.g., first and/or second structural color) can be considered as havinga “single” color when the change in color measured for the article iswithin about 10% or within about 5% of the total scale of the a* or b*coordinate of the L*a*b* scale (CIE 1976 color space) at three or moremeasured observation or illumination angles selected from measured atobservation or illumination angles of 0 degrees, 15 degrees, 30 degrees,45 degrees, 60 degrees, and −15 degrees. In certain embodiments, colorswhich, when measured and assigned values in the L*a*b* system thatdiffer by at least 5 percent of the scale of the a* and b* coordinates,or by at least 10 percent of the scale of the a* and b* coordinates, areconsidered to be different colors. The structurally-colored article canhave a change of less than about 40%, or less than about 30%, or lessthan about 20%, or less than about 10%, of the total scale of the a*coordinate or b* coordinate of the L*a*b* scale (CIE 1976 color space)at three or more measured observation or illumination angles.

Another example of a color scale is the CIELCH color space, where, for agiven illumination condition, L* is a value for lightness, C* is a valuefor chroma, and h° denotes a hue as an angular measurement. In anembodiment, a structural color (e.g., first and/or second structuralcolor) can be considered as having a “single” color when the colormeasured for the article is less than 10 degrees different or less than5 degrees different at the h° angular coordinate of the CIELCH colorspace, at three or more measured observation or illumination anglesselected from measured at observation or illumination angles of 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees. In certain embodiments, structure colors (e.g., first and/orsecond structural color) which, when measured and assigned values in theCIELCH system that vary by at least 45 degrees in the h° measurements,are considered to be different colors The structurally-colored articlecan have a change of 10 to about 60 degrees, 10 to about 50 degrees, or10 to about 40 degrees, 10 to about 30 degrees, or 10 to about 20degrees, in the h° measurements of the CIELCH system at three or moremeasured observation or illumination angles. The structurally-coloredarticle can have a change of about 1 to 10 degrees, about 1 to 7.5degrees, or 1 to about 2 degrees, in the h° measurements of the CIELCHsystem at three or more measured observation or illumination angles.

Another system for characterizing color includes the “PANTONE” MatchingSystem (Pantone LLC, Carlstadt, N.J., USA), which provides a visualcolor standard system to provide an accurate method for selecting,specifying, broadcasting, and matching colors through any medium. In anexample, a structurally-colored article having a structural color can beconsidered as having a “single” color when the color measured for thearticle is within a certain number of adjacent standards, e.g., within20 adjacent PANTONE standards, at three or more measured observation orillumination angles selected from 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, and −15 degrees.

A change or difference in color between two measurements and/or twocolors (e.g., first and/or second structural color) in the CIELAB spacecan be determined mathematically. For example, a first measurement(e.g., a first structural color) has coordinates L₁*, a₁* and b₁*, and asecond measurement (e.g., a second structural color) has coordinatesL₂*, a₂* and b₂*. The total difference between these two measurements onthe CIELAB scale can be expressed as ΔE*_(ab), which is calculated asfollows: ΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2). Generallyspeaking, if two colors (e.g., first and/or second structural color)have a ΔE*_(ab) of less than or equal to 1, the difference in color isnot perceptible to human eyes, and if two colors (e.g., first and/orsecond structural color) have a ΔE*_(ab) of greater than 100 the colorsare considered to be opposite colors, while a ΔE*_(ab) of about 2-3 isconsidered the threshold for perceivable color difference. In certainembodiments, a structurally colored article having structural color canbe considered as having a two colors when the ΔE*_(ab) of about 3 to 60,or about 3 to 50, or about 3 to 40, or about 3 to 30, between three ormore measured observation or illumination angles selected from measuredat observation or illumination angles of 0 degrees, 15 degrees, 30degrees, 45 degrees, 60 degrees, and −15 degrees. Thestructurally-colored article can have a ΔE*ab that is about 3 to about100, or about 3 to about 80, or about 3 to about 60, between two or moremeasured observation or illumination angles. In certain embodiments, astructurally colored article having structural color can be consideredas having a single color when the ΔE*_(ab) of about 1 to 3, or about 1to 2.5, or about 1 to 2.2, between three or more measured observation orillumination angles selected from measured at observation orillumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60degrees, and −15 degrees. In certain embodiments, a structurally coloredarticle having structural color can be considered as having a singlecolor when the ΔE*_(ab) of about 1 to 3, or about 1 to 2.5, or about 1to 2.2, between two or more measured observation or illumination anglesselected from measured at observation or illumination angles of 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees.

In regard to a potential difference between structural colors, theoptical element can have a first structural color on a first side and asecond structural color on a second side. The first structural color andthe second structural color can be different. The difference can bedetermined in the CIELAB space mathematically. For example, a firstmeasurement (e.g., obtained from the first side of the optical element)has coordinates L₁*, a₁* and b₁*, and a second measurement (e.g.,obtained from the second side of the optical element) has coordinatesL₂*, a₂* and b₂*. The total difference between these two measurements onthe CIELAB scale can be expressed as ΔE*_(ab), which is calculated asfollows: ΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2). Generallyspeaking, if two structural colors have a ΔE*_(ab) of less than or equalto 1, the difference in color is not perceptible to human eyes, and iftwo structural colors have a ΔE*_(ab) of greater than 100 the colors areconsidered to be opposite colors, while a ΔE*_(ab) of about 2-3 isconsidered the threshold for perceivable color difference and can dependupon the person perceiving the structural colors, the illuminationconditions, and the like. The first structural color and the secondstructural color can be different in that they can have a ΔE*_(ab) ofgreater than about 2.2, greater than about 3, greater than about 4,greater than about 5, or greater than about 10 or more. The firststructural color and the second structural color can be the same orsubstantially the same in that they can have a ΔE*_(ab) of less thanabout 3 or less than about 3. Since the threshold of perceivable colordifference is about 2-3 and the perception is depended upon the personperceiving, the conditions, and the like, the first structural color andthe second structural color may be subjectively the same or differentdepending upon the circumstance.

The method of making the structurally colored article can includedisposing (e.g., affixing, attaching, bonding, fastening, joining,appending, connecting, binding) the optical element onto an article(e.g., an article of footwear, an article of apparel, an article ofsporting equipment, etc.) in an “in-line” or “on its side”configuration. The article includes a component, and the component has asurface upon which the optical element can be disposed. The surface ofthe article can be made of a material such as a thermoplastic materialor thermoset material, as described herein. For example, the article hasa surface including a thermoplastic material (i.e., a firstthermoplastic material), for example an externally-facing surface of thecomponent or an internally-facing surface of the component (e.g., anexternally-facing surface or an internally-facing surface a bladder).The optical element can be disposed onto the thermoplastic material, forexample. The surface upon which the optical element is disposed is notopaque and is semi-transparent or transparent to light in from 380 to740 nanometers, for example, the surface can have a minimum percenttransmittance of about 30 percent or more, about 40 percent or more, orabout 50 percent or more, for light in the visible spectrum.

In an aspect, the temperature of at least a portion of the first surfaceof the article including the thermoplastic material is increased to atemperature at or above creep relaxation temperature (Tcr), Vicatsoftening temperature (Tvs), heat deflection temperature (Thd), and/ormelting temperature (Tm) of the thermoplastic material, for example tosoften or melt the thermoplastic material. The temperature can beincreased to a temperature at or above the creep relaxation temperature.The temperature can be increased to a temperature at or above the Vicatsoftening temperature. The temperature can be increased to a temperatureat or above the heat deflection temperature. The temperature can beincreased to a temperature at or above the melting temperature. Whilethe temperature of the at least a portion of the first side of thearticle is at or above the increased temperature (e.g., at or above thecreep relaxation temperature, the heat deflection temperature, the Vicatsoftening temperature, or the melting temperature of the thermoplasticmaterial), the optical element is affixed to the thermoplastic materialwithin the at least a portion of the first side of the article.Following the affixing, the temperature of the thermoplastic material isdecreased to a temperature below its creep relaxation temperature to atleast partially re-solidify the thermoplastic material. Thethermoplastic material can be actively cooled (e.g., removing the sourcethat increases the temperature and actively (e.g., flowing cooler gasadjacent the article reducing the temperature of the thermoplasticmaterial) or passively cooled (e.g., removing the source that increasesthe temperature and allowing the thermoplastic layer to cool on itsown).

Now having described color and other aspects generally, additionaldetails regarding the optical element are provided. As described herein,the article includes the optical element. The optical element includesat least one reflective layer (e.g., intermediate and/ornon-intermediate reflective layers) and at least one constituent layer.The optical element that can be or include a single layer reflector, asingle layer filter, or multilayer reflector or a multilayer filter. Theoptical element can function to modify the light that impinges thereuponso that structural color is imparted to the article. The optical elementcan also optionally include one or more additional layers (e.g., aprotective layer, the textured layer, a polymeric layer, and the like).The optical element can have a thickness of about 100 to 1,500nanometers, about 100 to 1,200 nanometers, about 100 to about 700nanometers, or of about 200 to about 500 nanometers.

The optical element has a first side (including the outer surface) and asecond side opposing the first side (including the opposing outersurface), where the first side or the second side is adjacent thearticle in the “in-line” configuration. In another configuration, theoptical element is in the “on its side” configuration where anouterside, in a plane perpendicular the plane of the first side and thesecond side, wherein the outerside is adjacent the article. The firstside of the optical element can impart the first structural color to thearticle while the second side of the optical element can impart thesecond structural color to the article. For example, when the opticalelement is used in conjunction with a component having internally-facingand externally-facing surfaces, such as a film or a bladder, either thefirst side or the second side of the optical element can be disposed onthe internally facing surface of the component, specifically if thefirst side of the optical element is disposed on the internally-facingsurface of the component, the configuration would have the followingorder: second side of the optical element/optical element/first side ofthe optical element/internally-facing surface of thecomponent/externally-facing surface of the component. In anotherexample, either the first side or the second side of the optical elementcan be disposed on the externally facing surface of the component, ifthe first side of the optical element is disposed on theexternally-facing surface of the component, the configuration would havethe following order: internally-facing surface of the component/core ofthe component/externally-facing surface of the component/first side ofthe optical element/optical element/second side of the optical element.In examples where the optional textured surface is present, the texturedsurface can be located at the interface between the surface of thecomponent and a side of the optical element.

The optical element or layers or portions thereof (e.g., reflectivelayer, constituent layer) can be formed using known techniques such asphysical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, pulsedlaser deposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), chemical vapor deposition,plasma-enhanced chemical vapor deposition, low pressure chemical vapordeposition and wet chemistry techniques such as layer-by-layerdeposition, sol-gel deposition, Langmuir blodgett, and the like. Thetemperature of the first side can be adjusted using the technique toform the optical element and/or a separate system to adjust thetemperature.

The optical element can comprise a single layer or multilayer reflector(e.g., reflective layer(s) and constituent layer(s)). The multilayerreflector can be configured to have a certain reflectivity at a givenwavelength of light (or range of wavelengths) depending, at least inpart, on the material selection, thickness and number of the layers ofthe multilayer reflector. In other words, one can carefully select thematerials, thicknesses, and numbers of the layers of a multilayerreflector and optionally its interaction with one or more other layers,so that it can reflect a certain wavelength of light (or range ofwavelengths), to produce a desired structural color. The optical elementcan include the first stack and the second stack and each have at leasttwo adjacent constituent layers, where the adjacent constituent layers(e.g., and the non-intermediate reflective layer(s) when present) havedifferent refractive indices. The difference in the index of refractionof adjacent layers of the constituent layer and the non-intermediatereflective layer when present can be about 0.0001 to 50 percent, about0.1 to 40 percent, about 0.1 to 30 percent, about 0.1 to 20 percent,about 0.1 to 10 percent (and other ranges there between (e.g., theranges can be in increments of 0.0001 to 5 percent)). The index ofrefraction depends at least in part upon the material of the constituentand can range from 1.3 to 2.6.

In each of the first stack and the second stack, the combination of thereflective(s) layer and the constituent layer(s) can include 2 to 20layers, 2 to 15, 2 to 10 layer, 2 to 6 layers, or 2 to 4 layers. Each ofthe reflective layer(s) or the constituent layer(s) can have a thicknessthat is about one-fourth of the wavelength of light to be reflected toproduce the desired structural color. Each of the reflective layer(s) orthe constituent layer(s) can have a thickness of about 10 to 500nanometers or about 90 to 200 nanometers. Each of the first stack andthe second stack of the optical element can have at least twoconstituent layers, where adjacent constituent layers have differentthicknesses and optionally the same or different refractive indices.

The optical element can comprise a single layer or multilayer filter.The multilayer filter destructively interferes with light that impingesupon the article, where the destructive interference of the light andoptionally interaction with one or more other layers or structures ofthe optical element (e.g., a multilayer reflector, a textured structure)impart the structural color. In this regard, the layers of themultilayer filter can be designed (e.g., material selection, thickness,number of layer, and the like) so that a single wavelength of light, ora particular range of wavelengths of light, make up the structuralcolor. For example, the range of wavelengths of light can be limited toa range within plus or minus 30 percent or a single wavelength, orwithin plus or minus 20 percent of a single wavelength, or within plusor minus 10 percent of a single wavelength, or within plus or minus 5percent or a single wavelength. The range of wavelengths can be broaderto produce a more iridescent structural color.

The reflective layer(s) and/or constituent layer(s) can include multiplelayers where each layer independently comprises a material selectedfrom: the transition metals, the metalloids, the lanthanides, and theactinides, as well as nitrides, oxynitrides, sulfides, sulfates,selenides, and tellurides of these, as well as others described herein.The reflective layer(s) and/or constituent layer(s) can be titanium,aluminum, silver, zirconium, chromium, magnesium, silicon, gold,platinum, and a combination thereof as well as oxides of each. Althoughthe reflective layer(s) and/or constituent layer(s) can be made of thesame material, the thickness of the layers can be different to producedifferent results. In one example, the intermediate reflective layer canbe thicker than the non-intermediate reflective layer and/or theconstituent layer(s).

The material for the constituent layer(s) can be selected to provide anindex of refraction that when optionally combined with the other layersof the optical element achieves the desired result. One or more layersof the constituent layer can be made of liquid crystals. Each layer ofthe constituent layer can be made of liquid crystals. One or more layersof the constituent layer can be made of a material such as: silicondioxide, titanium dioxide, zinc sulfide, magnesium fluoride, tantalumpentoxide, aluminum oxide, or a combination thereof. Each layer of theconstituent layer can be made of a material such as: silicon dioxide,titanium dioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide,aluminum oxide, or a combination thereof. To improve adhesion betweenlayers, a metal layer is adjacent a metal oxide layer formed of the samemetal. For example, Ti and TiO_(x) can be positioned adjacent oneanother to improve adhesion.

The optical element can be uncolored (e.g., no pigments or dyes added tothe structure or its layers), colored (e.g., pigments and/or dyes areadded to the structure or its layers (e.g., dark or black color)). Thesurface of the component upon which the optical element is disposed canbe uncolored (e.g., no pigments or dyes added to the material), colored(e.g., pigments and/or dyes are added to the material (e.g., dark orblack color)), reflective, and/or transparent (e.g., percenttransmittance of 75 percent or more).

The reflective layer(s) and/or the constituent layer(s) can be formed ina layer-by-layer manner, where each layer has a different index ofrefraction. Each of the reflective layer(s) and the constituent layer(s)can be formed using known techniques such as those described above andherein.

As mentioned above, the optical element can include the first stack andthe second stack, each independently can have one or more layers inaddition to the reflective layer(s) and the constituent layer(s). Theoptical element has a first side (e.g., the side having a surface) and asecond side (e.g., the side having a surface), where the first side orthe second side is adjacent the surface of the component. The one ormore other layers of the optical element can be on the first side and/orthe second side of the optical element. For example, the optical elementcan include a protective layer and/or a polymeric layer such as athermoplastic polymeric layer, where the protective layer and/or thepolymeric layer can be on one or both of the first side and the secondside of the optical element. One or more of the optional other layerscan include a textured surface. Alternatively or in addition, one ormore of the reflective layer(s) and/or one or more constituent layer(s)of the optical element can include a textured surface.

A protective layer can be disposed on the first and/or second side ofthe optical element, on the outside most constituent layer to protectthe constituent layer. The protective layer is more durable or moreabrasion resistant than the constituent layer. The protective layer isoptically transparent to visible light. The protective layer can be onthe first side and/or the second side of the optical element to protectthe constituent layers on the respective side. All or a portion of theprotective layer can include a dye or pigment in order to alter anappearance of the structural color. The protective layer can includesilicon dioxide, glass, combinations of metal oxides, or mixtures ofpolymers. The protective layer can have a thickness of about 3nanometers to 1 millimeter.

The protective layer can be formed using physical vapor deposition,chemical vapor deposition, pulsed laser deposition, evaporativedeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), plasma enhanced chemical vapordeposition, electron beam deposition, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett, andthe like. Alternatively or in addition, the protective layer can beapplied by spray coating, dip coating, brushing, spin coating, doctorblade coating, and the like.

A polymeric layer can be disposed on the first and/or the second side ofthe optical element. The polymeric layer can be used to dispose theoptical element onto an article, such as, for example, when the articledoes not include a thermoplastic material to adhere the optical element.The polymeric layer can comprise a polymeric adhesive material, such asa hot melt adhesive. The polymeric layer can be a thermoplastic materialand can include one or more layers. The thermoplastic material can beany one of the thermoplastic material described herein. The polymericlayer can be applied using various methodologies, such as spin coating,dip coating, doctor blade coating, and so on. The polymeric layer canhave a thickness of about 3 nanometer to 1 millimeter.

As described above, one or more embodiments of the present disclosureprovide articles that incorporate the optical element (e.g., single ormultilayer structures) on a side of a component of the article to impartstructural color. The optical element can be disposed onto thethermoplastic material of the side of the article, and the side of thearticle can include a textile, including a textile comprising thethermoplastic material Having described aspects, additional details willnow be described for the optional textured surface. As described herein,the component includes the optical element and the optical element caninclude at least one reflective layer and at least one constituent layerand optionally a textured surface. The textured surface can be a surfaceof a textured structure or a textured layer. The textured surface may beprovided as part of the optical element. For example, the opticalelement may comprise a textured layer or a textured structure thatcomprises the textured surface. The textured surface may be formed onthe intermediate reflective layer and/or the first and/or second side ofthe optical element. For example, a side of the reflective layer and/orthe constituent layer may be formed or modified to provide a texturedsurface, or a textured layer or textured structure can be affixed to thefirst or second side of the optical element. The textured surface may beprovided as part of the component to which the optical element isdisposed. For example, the optical element may be disposed onto thesurface of the component where the surface of the component is atextured surface, or the surface of the component includes a texturedstructure or a textured layer affixed to it.

The textured surface (or a textured structure or textured layerincluding the textured surface) may be provided as a feature on or partof another medium, such as a transfer medium, and imparted to a side orlayer of the optical element or to the surface of the component. Forexample, a mirror image or relief form of the textured surface may beprovided on the side of a transfer medium, and the transfer mediumcontacts a side of the optical element or the surface of the componentin a way that imparts the textured surface to the optical element orarticle. While the various embodiments herein may be described withrespect to a textured surface of the optical element, it will beunderstood that the features of the textured surface, or a texturedstructure or textured layer, may be imparted in any of these ways.

The textured surface can contribute to the structural color resultingfrom the optical element. As described herein, structural coloration isimparted, at least in part, due to optical effects caused by physicalphenomena such as scattering, diffraction, reflection, interference orunequal refraction of light rays from an optical element. The texturedsurface (or its mirror image or relief) can include a plurality ofprofile features and flat or planar areas. The plurality of profilefeatures included in the textured surface, including their size, shape,orientation, spatial arrangement, etc., can affect the light scattering,diffraction, reflection, interference and/or refraction resulting fromthe optical element. The flat or planar areas included in the texturedsurface, including their size, shape, orientation, spatial arrangement,etc., can affect the light scattering, diffraction, reflection,interference and/or refraction resulting from the optical element. Thedesired structural color can be designed, at least in part, by adjustingone or more of properties of the profile features and/or flat or planarareas of the textured surface.

The profile features can extend from a side of the flat areas, so as toprovide the appearance of projections and/or depressions therein. A flatarea can be a flat planar area. A profile feature may include variouscombinations of projections and depressions. For example, a profilefeature may include a projection with one or more depressions therein, adepression with one or more projections therein, a projection with oneor more further projections thereon, a depression with one or morefurther depressions therein, and the like. The flat areas do not have tobe completely flat and can include texture, roughness, and the like. Thetexture of the flat areas may not contribute much, if any, to theimparted structural color. The texture of the flat areas typicallycontributes to the imparted structural color. For clarity, the profilefeatures and flat areas are described in reference to the profilefeatures extending above the flat areas, but the inverse (e.g.,dimensions, shapes, and the like) can apply when the profile featuresare depressions in the textured surface.

The textured surface can comprise a thermoplastic material. The profilefeatures and the flat areas can be formed using a thermoplasticmaterial. For example, when the thermoplastic material is heated aboveits softening temperature a textured surface can be formed in thethermoplastic material such as by molding, stamping, printing,compressing, cutting, etching, vacuum forming, etc., the thermoplasticmaterial to form profile features and flat areas therein. The texturedsurface can be imparted on a side of a thermoplastic material. Thetextured surface can be formed in a layer of thermoplastic material. Theprofile features and the flat areas can be made of the samethermoplastic material or a different thermoplastic material.

The textured surface generally has a length dimension extending along anx-axis, and a width dimension extending along a z-axis, and a thicknessdimension extending along a y-axis. The textured surface has a generallyplanar portion extending in a first plane that extends along the x-axisand the z-axis. A profile feature can extend outward from the firstplane, so as to extend above or below the plane x. A profile feature mayextend generally orthogonal to the first plane, or at an angle greaterto or less than 90 degrees to the first plane.

The dimensional measurements in reference to the profile features (e.g.,length, width, height, diameter, and the like) described herein refer toan average dimensional measurement of profile features in 1 squarecentimeter in the inorganic optical element.

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. A textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers. The profile feature can have dimensions in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. All of the dimensions of the profile feature (e.g., length,width, height, diameter, depending on the geometry) can be in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. The textured surface can have a plurality of profilefeatures having dimensions that are 1 micrometer or less. In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have a dimension inthis range. The profile features can have a ratio of width:height and/orlength:height dimensions of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5and 1:10.

The textured surface can have a profile feature and/or flat area with adimension within the micrometer range of dimensions. A textured surfacecan have a profile feature and/or flat area with a dimension of about 1micrometer to about 500 micrometers. All of the dimensions of theprofile feature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, e.g., from about 1 micrometerto about 500 micrometers. The textured surface can have a plurality ofprofile features having dimensions that are from about 1 micrometer toabout 500 micrometer. In this context, the phrase “plurality of theprofile features” is meant to mean that about 50 percent or more, about60 percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have a dimension in this range. The height of the profilefeatures (or depth if depressions) can be about 0.1 and 50 micrometers,about 1 to 5 micrometers, or 2 to 3 micrometers. The profile featurescan have a ratio of width:height and/or length:height dimensions ofabout 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1:10.

A textured surface can have a plurality of profile features having amixture of size dimensions within the nanometer to micrometer range(e.g., a portion of the profile features are on the nanometer scale anda portion of the profile features are on the micrometer scale). Atextured surface can have a plurality of profile features having amixture of dimensional ratios. The textured surface can have a profilefeature having one or more nanometer-scale projections or depressions ona micrometer-scale projection or depression.

The profile feature can have height and width dimensions that are withina factor of three of each other (0.33w≤h≤3w where w is the width and his the height of the profile feature) and/or height and lengthdimensions that are within a factor of three of each other (0.331≤h≤3lwhere l is the length and h is the height of the profile feature). Theprofile feature can have a ratio of length:width that is from about 1:3to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1,or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of theprofile features can be substantially the same or different.

In another aspect, the textured surface can have a profile featureand/or flat area with at least one dimension in the mid-micrometer rangeand higher (e.g., greater than 500 micrometers). The profile feature canhave at least one dimension (e.g., the largest dimension such as length,width, height, diameter, and the like depending upon the geometry orshape of the profile feature) of greater than 500 micrometers, greaterthan 600 micrometers, greater than 700 micrometers, greater than 800micrometers, greater than 900 micrometers, greater than 1000micrometers, greater than 2 millimeters, greater than 10 millimeters, ormore. For example, the largest dimension of the profile feature canrange from about 600 micrometers to about 2000 micrometers, or about 650micrometers to about 1500 micrometers, or about 700 micrometers to about1000 micrometers. At least one or more of the dimensions of the profilefeature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, while one or more of the otherdimensions can be in the nanometer to micrometer range (e.g., less than500 micrometers, less than 100 micrometers, less than 10 micrometers, orless than 1 micrometer). The textured surface can have a plurality ofprofile features having at least one dimension that is in themid-micrometer or more range (e.g., 500 micrometers or more). In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have at least onedimension that is greater than 500 micrometers. In particular, at leastone of the length and width of the profile feature is greater than 500micrometers or both the length and the width of the profile feature isgreater than 500 micrometers. In another example, the diameter of theprofile feature is greater than 500 micrometers. In another example,when the profile feature is an irregular shape, the longest dimension isgreater than 500 micrometers.

In aspects, the height of the profile features can be greater than 50micrometers. In this context, the phrase “plurality of the profilefeatures” is meant to mean that about 50 percent or more, about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have at height that is greater than 50 micrometers. The heightof the profile feature can be 50 micrometers, about 60 micrometers,about 70 micrometers, about 80 micrometers, about 90 micrometers, orabout 100 micrometers to about 60 micrometers, about 70 micrometers,about 80 micrometers, about 90 micrometers, about 100 micrometers, about150 micrometers, about 250 micrometers, about 500 micrometers or more.For example, the ranges can include 50 micrometers to 500 micrometers,about 60 micrometers to 250 micrometers, about 60 micrometers to about150 micrometers, and the like. One or more of the other dimensions(e.g., length, width, diameter, or the like) can be in the nanometer tomicrometer range (e.g., less than 500 micrometers, less than 100micrometers, less than 10 micrometers, or less than 1 micrometer). Inparticular, at least one of the length and width of the profile featureis less than 500 micrometers or both the length and the width of theprofile feature is less than 500 micrometers, while the height isgreater than 50 micrometers. One or more of the other dimensions (e.g.,length, width, diameter, or the like) can be in the micrometer tomillimeter range (e.g., greater than 500 micrometers to 10 millimeters).

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. The textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers or higher (e.g., about 1 millimeter, about 2millimeters, about 5 millimeters, or about 10 millimeters). At least oneof the dimensions of the profile feature (e.g., length, width, height,diameter, depending on the geometry) can be in the nanometer range(e.g., from about 10 nanometers to about 1000 nanometers), while atleast one other dimension (e.g., length, width, height, diameter,depending on the geometry) can be in the micrometer range (e.g., 5micrometers to 500 micrometers or more (e.g., about 1 to 10millimeters)). The textured surface can have a plurality of profilefeatures having at least one dimension in the nanometer range (e.g.,about 10 to 1000 nanometers) and the other in the micrometer range(e.g., 5 micrometers to 500 micrometers or more). In this context, thephrase “plurality of the profile features” is meant to mean that about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more, or about 99 percentor more of the profile features have at least one dimension in thenanometer range and at least one dimension in the micrometer range. Inparticular, at least one of the length and width of the profile featureis in the nanometer range, while the other of the length and the widthof the profile feature is in the micrometer range.

In aspects, the height of the profile features can be greater than 250nanometers. In this context, the phrase “plurality of the profilefeatures” is meant to mean that about 50 percent or more, about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have at height that is greater than 250 nanometers. The heightof the profile feature can be 250 nanometers, about 300 nanometers,about 400 nanometers, or about 500 nanometers, to about 300 nanometers,about 400 nanometers, about 500 nanometers, or about 1000 nanometers ormore. For example, the range can be 250 nanometers to about 1000nanometers, about 300 nanometers to 500 nanometers, about 400 nanometersto about 1000 nanometers, and the like. One or more of the otherdimensions (e.g., length, width, diameter, or the like) can be in themicrometer to millimeter range (e.g., greater than 500 micrometers to 10millimeters). In particular, at least one of the length and width of theprofile feature is in the nanometer range (e.g., about 10 to 1000nanometers) and the other in the micrometer range (e.g., 5 micrometersto 500 micrometers or more), while the height is greater than 250nanometers.

The profile features can have a certain spatial arrangement. The spatialarrangement of the profile features may be uniform, such as spacedevenly apart or forming a pattern. The spatial arrangement can berandom. Adjacent profile features can be about 10 to 500 nanometersapart, about 100 to 1000 nanometers apart, about 1 to 100 micrometersapart or about 5 to 100 micrometers apart. Adjacent profile features canoverlap one another or be adjacent one another so little or no flatregions are positioned there between. The desired spacing can depend, atleast in part, on the size and/or shape of the profile structures andthe desired structural color effect.

The profile features can have a certain cross-sectional shape (withrespect to a plane parallel the first plane). The textured surface canhave a plurality of profile features having the same or similarcross-sectional shape. The textured surface has a plurality of profilefeatures having a mixture of different cross-sectional shapes. Thecross-sectional shapes of the profile features can include polygonal(e.g., square or triangle or rectangle cross section), circular,semi-circular, tubular, oval, random, high and low aspect ratios,overlapping profile features, and the like.

The profile feature (e.g., about 10 nanometers to 500 micrometers) caninclude an upper, flat surface. The profile feature (e.g., about 10nanometers to 500 micrometers) can include an upper, concavely curvedsurface. The concave curved surface may extend symmetrically either sideof an uppermost point. The concave curved surface may extendsymmetrically across only 50 percent of the uppermost point. The profilefeature (e.g., about 10 nanometers to 500 micrometers) can include anupper, convexly curved surface.

The curved surface may extend symmetrically either side of an uppermostpoint. The curved surface may extend symmetrically across only 50percent of the uppermost point. The profile feature can includeprotrusions from the textured surface. The profile feature can includeindents (hollow areas) formed in the textured surface. The profilefeature can have a smooth, curved shape (e.g., a polygonal cross-sectionwith curved corners).

The profile features (whether protrusions or depressions) can beapproximately conical or frusto-conical (i.e. the projections or indentsmay have horizontally or diagonally flattened tops) or have anapproximately part-spherical surface (e.g., a convex or concave surfacerespectively having a substantially even radius of curvature).

The profile features may have one or more sides or edges that extend ina direction that forms an angle to the first plane of the texturedsurface. The angle between the first plane and a side or edge of theprofile feature is about 45 degrees or less, about 30 degrees or less,about 25 degrees or less, or about 20 degrees or less. The one or moresides or edges may extend in a linear or planar orientation, or may becurved so that the angle changes as a function of distance from thefirst plane. The profile features may have one or more sides thatinclude step(s) and/or flat side(s). The profile feature can have one ormore sides (or portions thereof) that can be orthogonal or perpendicularto the first plane of the textured surface, or extend at an angle ofabout 10 degrees to 89 degrees to the first plane (90 degrees beingperpendicular or orthogonal to the first plane)). The profile featurecan have a side with a stepped configuration, where portions of the sidecan be parallel to the first plane of the textured surface or have anangle of about 1 degrees to 179 degrees (0 degrees being parallel to thefirst plane)).

The textured surface can have profile features with varying shapes(e.g., the profile features can vary in shape, height, width and lengthamong the profile features) or profile features with substantiallyuniform shapes and/or dimensions. The structural color produced by thetextured surface can be determined, at least in part, by the shape,dimensions, spacing, and the like, of the profile features.

The profile features can be shaped so as to result in a portion of thesurface (e.g., about 25 to 50 percent or more) being about normal to theincoming light when the light is incident at the normal to the firstplane of the textured surface. The profile features can be shaped so asto result in a portion of the surface (e.g., about 25 to 50 percent ormore) being about normal to the incoming light when the light isincident at an angle of up to 45 degrees to the first plane of thetextured surface.

The spatial orientation of the profile features on the textured surfacecan be used to produce the structural color, or to effect the degree towhich the structural color shifts at different viewing angles. Thespatial orientation of the profile features on the textured surface canbe random, a semi-random pattern, or in a set pattern. A set pattern ofprofile features is a known set up or configuration of profile featuresin a certain area (e.g., about 50 nanometers squared to about 10millimeters squared depending upon the dimensions of the profilefeatures (e.g., any increment between about 50 nanometers and about 10millimeters is included)). A semi-random pattern of profile features isa known set up of profile features in a certain area (e.g., about 50nanometers squared to 10 millimeters squared) with some deviation (e.g.,1 to 15% deviation from the set pattern), while random profile featuresare present in the area but the pattern of profile features isdiscernable. A random spatial orientation of the profile features in anarea produces no discernable pattern in a certain area, (e.g., about 50nanometers squared to 10 millimeters squared).

The spatial orientation of the profile features can be periodic (e.g.,full or partial) or non-periodic. A periodic spatial orientation of theprofile features is a recurring pattern at intervals. The periodicity ofthe periodic spatial orientation of the profile features can depend uponthe dimensions of the profile features but generally are periodic fromabout 50 nanometers to 100 micrometers. For example, when the dimensionsof the profile features are submicron, the periodicity of the periodicspatial orientation of the profile features can be in the 50 to 500nanometer range or 100 to 1000 nanometer range. In another example, whenthe dimensions of the profile features are at the micron level, theperiodicity of the periodic spatial orientation of the profile featurescan be in the 10 to 500 micrometer range or 10 to 1000 micrometer range.Full periodic pattern of profile features indicates that the entirepattern exhibits periodicity, whereas partial periodicity indicates thatless than all of the pattern exhibits periodicity (e.g., about 70-99percent of the periodicity is retained). A non-periodic spatialorientation of profile features is not periodic and does not showperiodicity based on the dimensions of the profile features, inparticular, no periodicity in the 50 to 500 nanometer range or 100 to1000 nanometer range where the dimensions are of the profile featuresare submicron or no periodicity in the 10 to 500 micrometer range or 10to 1000 micrometer range where the dimensions are of the profilefeatures are in the micron range.

In an aspect, the spatial orientation of the profile features on thetextured surface can be set to reduce distortion effects, e.g., causedby the interference of one profile feature with another in regard to thestructural color of the article. Since the shape, dimension, relativeorientation of the profile features can vary considerably across thetextured surface, the desired spacing and/or relative positioning for aparticular area (e.g., in the micrometer range or about 1 to 10 squaremicrometers) having profile features can be appropriately determined. Asdiscussed herein, the shape, dimension, relative orientation of theprofile features affect the contours of the reflective layer(s) and/orconstituent layer(s), so the dimensions (e.g., thickness), index ofrefraction, number of layers in the inorganic optical element (e.g.,reflective layer(s) and constituent layer(s)) are considered whendesigning the textured side of the texture layer.

The profile features are located in nearly random positions relative toone another across a specific area of the textured surface (e.g., in themicrometer range or about 1 to 10 square micrometers to centimeter rangeor about 0.5 to 5 square centimeters, and all range increments therein),where the randomness does not defeat the purpose of producing thestructural color. In other words, the randomness is consistent with thespacing, shape, dimension, and relative orientation of the profilefeatures, the dimensions (e.g., thickness), index of refraction, andnumber of layers (e.g., the reflective layer(s), the constituentlayer(s), and the like, with the goal to achieve the structural color.

The profile features are positioned in a set manner relative to oneanother across a specific area of the textured surface to achieve thepurpose of producing the structural color. The relative positions of theprofile features do not necessarily follow a pattern, but can follow apattern consistent with the desired structural color. As mentioned aboveand herein, various parameters related to the profile features, flatareas, and reflective layer(s) and/or the constituent layer can be usedto position the profile features in a set manner relative to oneanother.

The textured surface can include micro and/or nanoscale profile featuresthat can form gratings (e.g., a diffractive grating), photonic crystalstructure, a selective mirror structure, crystal fiber structures,deformed matrix structures, spiraled coiled structures, surface gratingstructures, and combinations thereof. The textured surface can includemicro and/or nanoscale profile features that form a grating having aperiodic or non-periodic design structure to impart the structuralcolor. The micro and/or nanoscale profile features can have apeak-valley pattern of profile features and/or flat areas to produce thedesired structural color. The grading can be an Echelette grating.

The profile features and the flat areas of the textured surface in theinorganic optical element can appear as topographical undulations ineach layer (e.g., reflective layer(s) and/or the constituent layer(s)).For example, referring to FIG. 2A, an inorganic optical element 200includes a textured structure 220 having a plurality of profile features222 and flat areas 224. As described herein, one or more of the profilefeatures 222 can be projections from a surface of the textured structure220, and/or one or more of the profile features can be depressions in asurface of the textured structure 220 (not shown). One or moreconstituent layers 240 are disposed on the textured structure 220 andthen a reflective layer 230 and one or more constituent layers 245 aredisposed on the preceding layers. In some embodiments, the resultingtopography of the textured structure 220 and the one or more constituentlayers 240 and 245 and the reflective layer 230 are not identical, butrather, the one or more constituent layers 240 and 245 and thereflective layer 230 can have elevated or depressed regions 242 whichare either elevated or depressed relative to the height of the planarregions 244 and which roughly correspond to the location of the profilefeatures 222 of the textured structure 220. The one or more constituentlayers 240 and 245 and the reflective layer 230 have planar regions 244that roughly correspond to the location of the flat areas 224 of thetextured structure 220. Due to the presence of the elevated or depressedregions 242 and the planar regions 244, the resultant overall topographyof the one or more constituent layers 240 and 245 and the reflectivelayer 230 can be that of an undulating or wave-like structure. Thedimension, shape, and spacing of the profile features along with thenumber of layers of the constituent layer, the reflective layer, thethickness of each of the layers, refractive index of each layer, and thetype of material, can be used to produce an inorganic optical elementwhich results in a particular structural color.

While the textured surface can produce the structural color in someembodiments, or can affect the degree to which the structural colorshifts at different viewing angles, in other embodiments, a “texturedsurface” or surface with texture may not produce the structural color,or may not affect the degree to which the structural color shifts atdifferent viewing angles. The structural color can be produced by thedesign of the inorganic optical element with or without the texturedsurface. As a result, the inorganic optical element can include thetextured surface having profile elements of dimensions in the nanometerto millimeter range, but the structural color or the shifting of thestructural color is not attributable to the presence or absence of thetextured surface. In other words, the inorganic optical element impartsthe same structural color where or not the textured surface is presentThe design of the textured surface can be configured to not affect thestructural color imparted by the inorganic optical element, or notaffect the shifting of the structural color imparted by the inorganicoptical element. The shape of the profile features, dimensions of theshapes, the spatial orientation of the profile features relative to oneanother, and the like can be selected so that the textured surface doesnot affect the structural color attributable to the inorganic opticalelement.

The structural color imparted by a first inorganic optical element and asecond inorganic optical element, where the only difference between thefirst and second inorganic optical element is that the first inorganicoptical element includes the textured surface, can be compared. A colormeasurement can be performed for each of the first and second inorganicoptical element at the same relative angle, where a comparison of thecolor measurements can determine what, if any, change is correlated tothe presence of the textured surface. For example, at a firstobservation angle the structural color is a first structural color forthe first inorganic optical element and at first observation angle thestructural color is a second structural color for the second inorganicoptical element. The first color measurement can be obtained and hascoordinates L₁* and a₁* and b₁*, while a second color measurement can beobtained and has coordinates L₂* and a₂* and b₂* can be obtained,according to the CIE 1976 color space under a given illuminationcondition.

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first structural color associated with the first colormeasurement and the second structural color associated with the secondcolor measurement are the same or not perceptibly different to anaverage observer (e.g., the textured surface does not cause or changethe structural color by more than 20 percent, 10 percent, or 5 percent).When ΔE*_(ab) between the first color measurement and the second colormeasurement is greater than 3 or optionally greater than about 4 or 5,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are different or perceptibly different to an averageobserver (e.g., the textured surface does cause or change the structuralcolor by more than 20 percent, 10 percent, or 5 percent).

In another approach, when the percent difference between one or more ofvalues L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is less than 20 percent,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are the same or not perceptibly different to an averageobserver (e.g., the textured surface does not cause or change thestructural color by less than 20 percent, 10 percent, or 5 percent).When the percent difference between one or more of values L₁* and L₂*a₁* and a₂*, and b₁* and b₂* is greater than 20 percent, the firststructural color associated with the first color measurement and thesecond structural color associated with the second color measurement aredifferent or perceptibly different to an average observer (e.g., thetextured surface does cause or change the structural color by more than20 percent, 10 percent, or 5 percent).

In another case, the structural color imparted by a first inorganicoptical element and a second inorganic optical element, where the onlydifferent between the first and second inorganic optical element is thatthe first inorganic optical element includes the textured surface, canbe compared at different angles of incident light upon the inorganicoptical element or different observation angles. A color measurement canbe performed for each of the first and second inorganic optical elementat different angles (e.g., angle of about −15 and 180 degrees or about−15 degrees and +60 degrees and which are at least 15 degrees apart fromeach other), where a comparison of the color measurements can determinewhat, if any, change is correlated to the presence of the texturedsurface a different angles. For example, at a first observation anglethe structural color is a first structural color for the first inorganicoptical element and at second observation angle the structural color isa second structural color for the second inorganic optical element. Thefirst color measurement can be obtained and has coordinates L₁* and a₁*and b₁*, while a second color measurement can be obtained and hascoordinates L₂* and a₂* and b₂* can be obtained, according to the CIE1976 color space under a given illumination condition.

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first structural color associated with the first colormeasurement and the second structural color associated with the secondcolor measurement are the same or not perceptibly different to anaverage observer (e.g., the textured surface does not cause or changethe structural color based on different angles of incident light uponthe inorganic optical element or different observation angles). WhenΔE*_(ab) between the first color measurement and the second colormeasurement is greater than 3 or optionally greater than about 4 or 5,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are different or perceptibly different to an averageobserver (e.g., the textured surface does cause or change the structuralcolor at different angles of incident light upon the inorganic opticalelement or different observation angles).

In another approach, when the percent difference between one or more ofvalues L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is less than 20 percent,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are the same or not perceptibly different to an averageobserver (e.g., the textured surface does not cause or change thestructural color by more than 20 percent, 10 percent, or 5 percent atdifferent angles of incident light upon the inorganic optical element ordifferent observation angles). When the percent difference between oneor more of values L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is greaterthan 20 percent, the first structural color associated with the firstcolor measurement and the second structural color associated with thesecond color measurement are different or perceptibly different to anaverage observer (e.g., the textured surface does cause or change thestructural color by more than 20 percent, 10 percent, or 5 percent atdifferent angles of incident light upon the inorganic optical element ordifferent observation angles).

In another embodiment, the structural color can be imparted by theinorganic optical element without the textured surface. The surface ofthe layers of the optical element are substantially flat (orsubstantially three dimensional flat planar surface) or flat (or threedimensional flat planar surface) at the microscale (e.g., about 1 to 500micrometers) and/or nanoscale (e.g., about 50 to 500 nanometers). Inregard to substantially flat or substantially planar the surface caninclude some minor topographical features (e.g., nanoscale and/ormicroscale) such as those that might be caused due to unintentionalimperfections, slight undulations that are unintentional, othertopographical features (e.g., extensions above the plane of the layer ordepressions below or into the plane of the layer) caused by theequipment and/or process used and the like that are unintentionallyintroduced. The topographical features do not resemble profile featuresof the textured surface. In addition, the substantially flat (orsubstantially three dimensional flat planar surface) or flat (or threedimensional flat planar surface) may include curvature as the dimensionsof the optical element increase, for example about 500 micrometers ormore, about 10 millimeter or more, about 10 centimeters or more,depending upon the dimensions of the inorganic optical element, as longas the surface is flat or substantially flat and the surface onlyincludes some minor topographical features.

FIG. 2B is a cross-section illustration of a substantially flat (orsubstantially three dimensional flat planar surface) or flat (or threedimensional flat planar surface) inorganic optical element 300. Theinorganic optical element 300 includes one or more constituent layers340 are disposed on the flat or three dimensional flat planar surfacestructure 320 and then a reflective layer 330 and one or moreconstituent layers 345 are disposed on the preceding layers. Thematerial that makes up the constituent layers and the reflective layer,number of layers of the constituent layer, the reflective layer, thethickness of each of the layers, refractive index of each layer, and thelike, can produce an inorganic optical element which results in aparticular structural color.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe article, components of the article, structures, layers, films,bladders, foams, coating, and like the. The polymer can be a thermosetpolymer or a thermoplastic polymer. The polymer can be an elastomericpolymer, including an elastomeric thermoset polymer or an elastomericthermoplastic polymer. The polymer can be selected from: polyurethanes(including elastomeric polyurethanes, thermoplastic polyurethanes(TPUs), and elastomeric TPUs), polyesters, polyethers, polyamides, vinylpolymers (e.g., copolymers of vinyl alcohol, vinyl esters, ethylene,acrylates, methacrylates, styrene, and so on), polyacrylonitriles,polyphenylene ethers, polycarbonates, polyureas, polystyrenes,co-polymers thereof (including polyester-polyurethanes,polyether-polyurethanes, polycarbonate-polyurethanes, polyether blockpolyamides (PEBAs), and styrene block copolymers), and any combinationthereof, as described herein. The polymer can include one or morepolymers selected from the group consisting of polyesters, polyethers,polyamides, polyurethanes, polyolefins copolymers of each, andcombinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

As previously described, the polymer can be a thermoplastic polymer. Ingeneral, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm3/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm3/10 min to about 28 cm3/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

The polymer can be a thermoset polymer. As used herein, a “thermosetpolymer” is understood to refer to a polymer which cannot be heated andmelted, as its melting temperature is at or above its decompositiontemperature. A “thermoset material” refers to a material which comprisesat least one thermoset polymer. The thermoset polymer and/or thermosetmaterial can be prepared from a precursor (e.g., an uncured or partiallycured polymer or material) using thermal energy and/or actinic radiation(e.g., ultraviolet radiation, visible radiation, high energy radiation,infrared radiation) to form a partially cured or fully cured polymer ormaterial which no longer remains fully thermoplastic. In some cases, thecured or partially cured polymer or material may remain thermoelasticproperties, in that it is possible to partially soften and mold thepolymer or material at elevated temperatures and/or pressures, but it isnot possible to melt the polymer or material. The curing can bepromoted, for example, with the use of high pressure and/or a catalyst.In many examples, the curing process is irreversible since it results incross-linking and/or polymerization reactions of the precursors. Theuncured or partially cured polymers or materials can be malleable orliquid prior to curing. In some cases, the uncured or partially curedpolymers or materials can be molded into their final shape, or used asadhesives. Once hardened, a thermoset polymer or material cannot bere-melted in order to be reshaped. The textured surface can be formed bypartially or fully curing an uncured precursor material to lock in thetextured surface.

Polyurethane

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Alternatively, the polymer can be athermoset polyurethane. Additionally, polyurethane can be an elastomericpolyurethane, including an elastomeric TPU or an elastomeric thermosetpolyurethane. The elastomeric polyurethane can include hard and softsegments. The hard segments can comprise or consist of urethane segments(e.g., isocyanate-derived segments). The soft segments can comprise orconsist of alkoxy segments (e.g., polyol-derived segments includingpolyether segments, or polyester segments, or a combination of polyethersegments and polyester segments). The polyurethane can comprise orconsist essentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R1 group and R2 group independently is an aliphatic or aromaticgroup. Optionally, each R2 can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R3 includes the chain extender.As with each R1 and R2, each R3 independently is an aliphatic oraromatic functional group.

Each R1 group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R1 group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R1 groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R1group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term Cn it meansthe alkene or alkylene group has “n” carbon atoms. For example, C1-6alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5, or 6carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R1 group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. Thepolymer chains can be substantially free of aromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H12 aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H12aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R3 group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R2 group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R2 group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R2 group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term Cn it means the alkyl group has “n” carbonatoms. For example, C4 alkyl refers to an alkyl group that has 4 carbonatoms. C1-7 alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R2 group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol 1,5-diethylene glycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R2 group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol 1,5-diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkenylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkenylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R2 group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R2 is an aliphatic or aromatic group having pendant amino,carboxylate, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R2 group in the polyurethane can include apolytetramethylene oxide group. At least one R2 group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in E.P. Patent No. 2 462 908, which is herebyincorporated by reference. For example, the R2 group can be derived fromthe reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

At least one R2 of the polyurethane can be a polysiloxane, In thesecases, the R2 group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R4 independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R5 independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R4 group can independently be a H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R4 group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R5 group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R5 group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R5 group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). The crosslinked polyurethanecan be a thermoset polymer. This crosslinked polymeric network can beproduced by polymerizing one or more isocyanates with one or morepolyamino compounds, polysulfhydryl compounds, or combinations thereof,as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R1 group in Formula 1, and the R1 and R3 groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R2 group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

The polyurethane can be a thermoplastic polyurethane composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, Ill., USA), “PELLETHANE” 2355-85ATP and2355-95AE (Dow Chemical Company of Midland, Mich., USA.), “ESTANE”(e.g., ALR G 500, or 58213; Lubrizol, Countryside, Ill., USA).

One or more of the polyurethanes (e.g., water-dispersible polyurethane))can be produced by polymerizing one or more isocyanates with one or morepolyols to produce copolymer chains having carbamate linkages(—N(C═O)O—) and one or more water-dispersible enhancing moieties, wherethe polymer chain includes one or more water-dispersible enhancingmoieties (e.g., a monomer in polymer chain). The water-dispersiblepolyurethane can also be referred to as “a water-borne polyurethanepolymer dispersion.” The water-dispersible enhancing moiety can be addedto the chain of Formula 1 or 2 (e.g., within the chain and/or onto thechain as a side chain). Inclusion of the water-dispersible enhancingmoiety enables the formation of a water-borne polyurethane dispersion.The term “water-borne” herein means the continuous phase of thedispersion or formulation of about 50 weight percent to 100 weightpercent water, about 60 weight percent to 100 weight percent water,about 70 weight percent to 100 weight percent water, or about 100 weightpercent water. The term “water-borne dispersion” refers to a dispersionof a component (e.g., polymer, cross-linker, and the like) in waterwithout co-solvents. The co-solvent can be used in the water-bornedispersion and the co-solvent can be an organic solvent. Additionaldetail regarding the polymers, polyurethanes, isocyantes and the polyolsare provided below.

The polyurethane (e.g., a water-borne polyurethane polymer dispersion)can include one or more water-dispersible enhancing moieties. Thewater-dispersible enhancing moiety can have at least one hydrophilic(e.g., poly(ethylene oxide)), ionic or potentially ionic group to assistdispersion of the polyurethane, thereby enhancing the stability of thedispersions. A water-dispersible polyurethane can be formed byincorporating a moiety bearing at least one hydrophilic group or a groupthat can be made hydrophilic (e.g., by chemical modifications such asneutralization) into the polymer chain. For example, these compounds canbe nonionic, anionic, cationic or zwitterionic or the combinationthereof. In one example, anionic groups such as carboxylic acid groupscan be incorporated into the chain in an inactive form and subsequentlyactivated by a salt-forming compound, such as a tertiary amine. Otherwater-dispersible enhancing moieties can also be reacted into thebackbone through urethane linkages or urea linkages, including lateralor terminal hydrophilic ethylene oxide or ureido units.

The water-dispersible enhancing moiety can be a one that includescarboxyl groups. Water-dispersible enhancing moiety that include acarboxyl group can be formed from hydroxy-carboxylic acids having thegeneral formula (HO)xQ(COOH)y, where Q can be a straight or branchedbivalent hydrocarbon radical containing 1 to 12 carbon atoms, and x andy can each independently be 1 to 3. Illustrative examples includedimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), citricacid, tartaric acid, glycolic acid, lactic acid, malic acid,dihydroxymalic acid, dihydroxytartaric acid, and the like, and mixturesthereof.

The water-dispersible enhancing moiety can include reactive polymericpolyol components that contain pendant anionic groups that can bepolymerized into the backbone to impart water dispersiblecharacteristics to the polyurethane. Anionic functional polymericpolyols can include anionic polyester polyols, anionic polyetherpolyols, and anionic polycarbonate polyols, where additional detail isprovided in U.S. Pat. No. 5,334,690.

The water-dispersible enhancing moiety can include a side chainhydrophilic monomer. For example, the water-dispersible enhancing moietyincluding the side chain hydrophilic monomer can include alkylene oxidepolymers and copolymers in which the alkylene oxide groups have from2-10 carbon atoms as shown in U.S. Pat. No. 6,897,281. Additional typesof water-dispersible enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide,or a thermoset polyamide. The polyamide can be an elastomeric polyamide,including an elastomeric thermoplastic polyamide or an elastomericthermoset polyamide. The polyamide can be a polyamide homopolymer havingrepeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R6 group represents the portion of thepolyamide derived from the lactam or amino acid.

The R6 group can be derived from a lactam. The R6 group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R6 group can be derived from caprolactam orlaurolactam. The R6 group can be derived from one or more amino acids.The R6 group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R6 groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R7 group represents the portion of thepolyamide derived from the diamino compound, and the R8 group representsthe portion derived from the dicarboxylic acid compound:

The R7 group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R7 group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD), m-xylylene diamine (MXD), and1,5-pentamine diamine. The R8 group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR8 can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R8 can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an α, ω-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH2)10-COOH can be used; and a lactam such as caprolactam andlauryllactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine such as an aliphatic diaminecontaining from 6 to 12 atoms and can be acyclic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α, ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 Pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)₄, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies. In other cases, the crosslinked polyamide is a thermosetpolymer.

Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester, or a thermoset polyester. Additionally, thepolyester can be an elastomeric polyester, including a thermoplasticpolyester or a thermoset elastomeric polyester. The polyester can beformed by reaction of one or more carboxylic acids, or its ester-formingderivatives, with one or more bivalent or multivalent aliphatic,alicyclic, aromatic or araliphatic alcohols or a bisphenol. Thepolyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester.

The co-polyester can be formed from the polycondensation of a polyesteroligomer or prepolymer with a second oligomer prepolymer to form a blockcopolyester. Optionally, the second prepolymer can be a hydrophilicprepolymer. For example, the co-polyester can be formed from thepolycondensation of terephthalic acid or naphthalene dicarboxylic acidwith ethylene glycol, 1,4-butanediol, or 1,3-propanediol. Examples ofco-polyesters include polyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(α-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin or a thermoset polyolefin.Additionally, the polyolefin can be an elastomeric polyolefin, includinga thermoplastic elastomeric polyolefin or a thermoset elastomericpolyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g., metallocene-catalyzed blockcopolymers of ethylene and α-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, a ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, VIb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, VIb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic and/or thermosetting material can further comprise oneor more processing aids. The processing aid can be a non-polymericmaterial. These processing aids can be independently selected from thegroup including, but not limited to, curing agents, initiators,plasticizers, mold release agents, lubricants, antioxidants, flameretardants, dyes, pigments, reinforcing and non-reinforcing fillers,fiber reinforcements, and light stabilizers.

In articles that include a textile, the optical element can be disposedonto the textile (e.g., the optical element is likely in the “on itsside” configuration unless the textile is thin or otherwise the firstside of the optical element can be illuminated). The textile or at leastan outer layer of the textile can include a thermoplastic material thatthe optical element can disposed onto. The textile can be a nonwoventextile, a synthetic leather, a knit textile, or a woven textile. Thetextile can comprise a first fiber or a first yarn, where the firstfiber or the first yarn can include at least an outer layer formed ofthe first thermoplastic material. A region of the first or second sideof the structure onto which the optical element is disposed can includethe first fiber or the first yarn in a non-filamentous conformation. Theoptical element can be disposed onto the textile or the textile can beprocessed so that the optical element can be disposed onto the textile.The textured surface can be made of or formed from the textile surface.The textile surface can be used to form the textured surface, and eitherbefore or after this, the optical element can be applied to the textile.

A “textile” may be defined as any material manufactured from fibers,filaments, or yarns characterized by flexibility, fineness, and a highratio of length to thickness. Textiles generally fall into twocategories. The first category includes textiles produced directly fromwebs of filaments or fibers by randomly interlocking to constructnon-woven fabrics and felts. The second category includes textilesformed through a mechanical manipulation of yarn, thereby producing awoven fabric, a knitted fabric, a braided fabric, a crocheted fabric,and the like.

The terms “filament,” “fiber,” or “fibers” as used herein refer tomaterials that are in the form of discrete elongated pieces that aresignificantly longer than they are wide. The fiber can include natural,manmade or synthetic fibers. The fibers may be produced by conventionaltechniques, such as extrusion, electrospinning, interfacialpolymerization, pulling, and the like. The fibers can include carbonfibers, boron fibers, silicon carbide fibers, titania fibers, aluminafibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, andNE glasses and quartz, or the like. The fibers can be fibers formed fromsynthetic polymers capable of forming fibers such as poly(ether ketone),polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters,polyolefins (e.g., polyethylene, polypropylene), aromatic polyamides(e.g., an aramid polymer such as para-aramid fibers and meta-aramidfibers), aromatic polyimides, polybenzimidazoles, polyetherimides,polytetrafluoroethylene, acrylic, modacrylic, poly(vinyl alcohol),polyamides, polyurethanes, and copolymers such as polyether-polyureacopolymers, polyester-polyurethanes, polyether block amide copolymers,or the like. The fibers can be natural fibers (e.g., silk, wool,cashmere, vicuna, cotton, flax, hemp, jute, sisal). The fibers can beman-made fibers from regenerated natural polymers, such as rayon,lyocell, acetate, triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made andsynthetic fibers are generally extruded in substantially continuousstrands. Alternatively, the fibers can be staple fibers, such as, forexample, cotton fibers or extruded synthetic polymer fibers can be cutto form staple fibers of relatively uniform length. The staple fiber canhave a have a length of about 1 millimeter to 100 centimeters or more aswell as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Naturalfibers can have a natural cross-section, or can have a modifiedcross-sectional shape (e.g., with processes such as mercerization).Man-made or synthetic fibers can be extruded to provide a strand havinga predetermined cross-sectional shape. The cross-sectional shape of afiber can affect its properties, such as its softness, luster, andwicking ability. The fibers can have round or essentially round crosssections. Alternatively, the fibers can have non-round cross sections,such as flat, oval, octagonal, rectangular, wedge-shaped, triangular,dog-bone, multi-lobal, multi-channel, hollow, core-shell, or othershapes.

The fiber can be processed. For example, the properties of fibers can beaffected, at least in part, by processes such as drawing (stretching)the fibers, annealing (hardening) the fibers, and/or crimping ortexturizing the fibers.

In some cases a fiber can be a multi-component fiber, such as onecomprising two or more co-extruded polymeric materials. The two or moreco-extruded polymeric materials can be extruded in a core-sheath,islands-in-the-sea, segmented-pie, striped, or side-by-sideconfiguration. A multi-component fiber can be processed in order to forma plurality of smaller fibers (e.g., microfibers) from a single fiber,for example, by remove a sacrificial material.

The fiber can be a carbon fiber such as TARIFYL produced by FormosaPlastics Corp. of Kaohsiung City, Taiwan, (e.g., 12,000, 24,000, and48,000 fiber tows, specifically fiber types TC-35 and TC-35R), carbonfiber produced by SGL Group of Wiesbaden, Germany (e.g., 50,000 fibertow), carbon fiber produced by Hyosung of Seoul, South Korea, carbonfiber produced by Toho Tenax of Tokyo, Japan, fiberglass produced byJushi Group Co., LTD of Zhejiang, China (e.g., E6, 318, silane-basedsizing, filament diameters 14, 15, 17, 21, and 24 micrometers), andpolyester fibers produced by Amann Group of Bonningheim, Germany (e.g.,SERAFILE 200/2 non-lubricated polyester filament and SERAFILE COMPHIL200/2 lubricated polyester filament).

A plurality of fibers includes 2 to hundreds or thousands or morefibers. The plurality of fibers can be in the form of bundles of strandsof fibers, referred to as tows, or in the form of relatively alignedstaple fibers referred to as sliver and roving. A single type fiber canbe used either alone or in combination with one or more different typesof fibers by co-mingling two or more types of fibers. Examples ofco-mingled fibers include polyester fibers with cotton fibers, glassfibers with carbon fibers, carbon fibers with aromatic polyimide(aramid) fibers, and aromatic polyimide fibers with glass fibers.

As used herein, the term “yarn” refers to an assembly formed of one ormore fibers, wherein the strand has a substantial length and arelatively small cross-section, and is suitable for use in theproduction of textiles by hand or by machine, including textiles madeusing weaving, knitting, crocheting, braiding, sewing, embroidery, orropemaking techniques. Thread is a type of yarn commonly used forsewing.

Yarns can be made using fibers formed of natural, man-made and syntheticmaterials. Synthetic fibers are most commonly used to make spun yarnsfrom staple fibers, and filament yarns. Spun yarn is made by arrangingand twisting staple fibers together to make a cohesive strand. Theprocess of forming a yarn from staple fibers typically includes cardingand drawing the fibers to form sliver, drawing out and twisting thesliver to form roving, and spinning the roving to form a strand.Multiple strands can be plied (twisted together) to make a thicker yarn.The twist direction of the staple fibers and of the plies can affect thefinal properties of the yarn. A filament yarn can be formed of a singlelong, substantially continuous filament, which is conventionallyreferred to as a “monofilament yarn,” or a plurality of individualfilaments grouped together. A filament yarn can also be formed of two ormore long, substantially continuous filaments which are grouped togetherby grouping the filaments together by twisting them or entangling themor both. As with staple yarns, multiple strands can be plied together toform a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing,thermal or mechanical treating, or coating with a material such as asynthetic polymer. The fibers, yarns, or textiles, or any combinationthereof, used in the disclosed articles can be sized. Sized fibers,yarns, and/or textiles are coated on at least part of their surface witha sizing composition selected to change the absorption or wearcharacteristics, or for compatibility with other materials. The sizingcomposition facilitates wet-out and wet-through of the coating or resinupon the surface and assists in attaining desired physical properties inthe final article. An exemplary sizing composition can comprise, forexample, epoxy polymers, urethane-modified epoxy polymers, polyesterpolymers, phenol polymers, polyamide polymers, polyurethane polymers,polycarbonate polymers, polyetherimide polymers, polyamideimidepolymers, polystylylpyridine polymers, polyimide polymers bismaleimidepolymers, polysulfone polymers, polyethersulfone polymers,epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarnssuch as single- or double-covered yarns, and corespun yarns.Accordingly, yarns may have a variety of configurations that generallyconform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one ormore of the fibers can be made of thermoplastic material). The yarn canbe made of a thermoplastic material. The yarn can be coated with a layerof a material such as a thermoplastic material.

The linear mass density or weight per unit length of a yarn can beexpressed using various units, including denier (D) and tex. Denier isthe mass in grams of 9000 meters of yarn. The linear mass density of asingle filament of a fiber can also be expressed using denier perfilament (DPF). Tex is the mass in grams of a 1000 meters of yarn.Decitex is another measure of linear mass, and is the mass in grams fora 10,000 meters of yarn.

As used herein, tenacity is understood to refer to the amount of force(expressed in units of weight, for example: pounds, grams, centinewtonsor other units) needed to break a yarn (i.e., the breaking force orbreaking point of the yarn), divided by the linear mass density of theyarn expressed, for example, in (unstrained) denier, decitex, or someother measure of weight per unit length. The breaking force of the yarnis determined by subjecting a sample of the yarn to a known amount offorce, for example, using a strain gauge load cell such as an INSTRONbrand testing system (Norwood, Mass., USA). Yarn tenacity and yarnbreaking force are distinct from burst strength or bursting strength ofa textile, which is a measure of how much pressure can be applied to thesurface of a textile before the surface bursts.

Generally, in order for a yarn to withstand the forces applied in anindustrial knitting machine, the minimum tenacity required isapproximately 1.5 grams per Denier. Most yarns formed from commoditypolymeric materials generally have tenacities in the range of about 1.5grams per Denier to about 4 grams per Denier. For example, polyesteryarns commonly used in the manufacture of knit uppers for footwear havetenacities in the range of about 2.5 to about 4 grams per Denier. Yarnsformed from commodity polymeric materials which are considered to havehigh tenacities generally have tenacities in the range of about 5 gramsper Denier to about 10 grams per Denier. For example, commerciallyavailable package dyed polyethylene terephthalate yarn from NationalSpinning (Washington, N.C., USA) has a tenacity of about 6 grams perDenier, and commercially available solution dyed polyethyleneterephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has atenacity of about 7 grams per Denier. Yarns formed from high performancepolymeric materials generally have tenacities of about 11 grams perDenier or greater. For example, yarns formed of aramid fiber typicallyhave tenacities of about 20 grams per Denier, and yarns formed ofultra-high molecular weight polyethylene (UHMWPE) having tenacitiesgreater than 30 grams per Denier are available from Dyneema (Stanley,N.C., USA) and Spectra (Honeywell-Spectra, Colonial Heights, Va., USA).

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The yarns utilized in interweaving are conventionallyreferred to as “warp” and “weft.” A woven textile includes include awarp yarn and a weft yarn. The warp yarn extends in a first direction,and the weft strand extends in a second direction that is substantiallyperpendicular to the first direction. Intertwining and twistingencompasses various procedures, such as braiding and knotting, whereyarns intertwine with each other to form a textile. Interloopinginvolves the formation of a plurality of columns of intermeshed loops,with knitting being the most common method of interlooping. The textilemay be primarily formed from one or more yarns that aremechanically-manipulated, for example, through interweaving,intertwining and twisting, and/or interlooping processes, as mentionedabove.

The textile can be a nonwoven textile. Generally, a nonwoven textile orfabric is a sheet or web structure made from fibers and/or yarns thatare bonded together. The bond can be a chemical and/or mechanical bond,and can be formed using heat, solvent, adhesive or a combinationthereof. Exemplary nonwoven fabrics are flat or tufted porous sheetsthat are made directly from separate fibers, molten plastic and/orplastic film. They are not made by weaving or knitting and do notnecessarily require converting the fibers to yarn, although yarns can beused as a source of the fibers. Nonwoven textiles are typicallymanufactured by putting small fibers together in the form of a sheet orweb (similar to paper on a paper machine), and then binding them eithermechanically (as in the case of felt, by interlocking them with serratedor barbed needles, or hydro-entanglement such that the inter-fiberfriction results in a stronger fabric), with an adhesive, or thermally(by applying binder (in the form of powder, paste, or polymer melt) andmelting the binder onto the web by increasing temperature). A nonwoventextile can be made from staple fibers (e.g., from wetlaid, airlaid,carding/crosslapping processes), or extruded fibers (e.g., frommeltblown or spunbond processes, or a combination thereof), or acombination thereof. Bonding of the fibers in the nonwoven textile canbe achieved with thermal bonding (with or without calendering),hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting),chemical bonding (e.g., using binders such as latex emulsions orsolution polymers or binder fibers or powders), meltblown bonding (e.g.,fiber is bonded as air attenuated fibers intertangle during simultaneousfiber and web formation).

Now having described various aspects of the present disclosure,additional discussion is provided regarding when the optical element isused in conjunction with a bladder. The bladder can be unfilled,partially inflated, or fully inflated when the optical element isdisposed onto the bladder. The bladder is a bladder capable of includinga volume of a fluid. An unfilled bladder is a fluid-fillable bladder anda filled bladder that has been at least partially inflated with a fluidat a pressure equal to or greater than atmospheric pressure. Whendisposed onto or incorporated into an article of footwear, apparel, orsports equipment, the bladder is generally, at that point, afluid-filled bladder. The fluid be a gas or a liquid. The gas caninclude air, nitrogen gas (N₂), or other appropriate gas.

The bladder can have a gas transmission rate for nitrogen gas, forexample, where a bladder wall of a given thickness has a gastransmission rate for nitrogen that is at least about ten times lowerthan the gas transmission rate for nitrogen of a butyl rubber layer ofsubstantially the same thickness as the thickness of the bladderdescribed herein. The bladder can have a first bladder wall having afirst bladder wall thickness (e.g., about 0.1 to 40 mils). The bladdercan have a first bladder wall that can have a gas transmission rate(GTR) for nitrogen gas of less than about 15 cm³/m²·atm·day, less thanabout 10 m³/m²·atm·day, less than about 5 cm³/m²·atm·day, less thanabout 1 cm³/m²·atm·day (e.g., from about 0.001 cm³/m²·atm·day to about 1cm³/m²·atm·day, about 0.01 cm³/m²·atm·day to about 1 cm³/m²·atm·day orabout 0.1 cm³/m²·atm·day to about 1 cm³/m²·atm·day) for an average wallthickness of 20 mils. The bladder can have a first bladder wall having afirst bladder wall thickness, where the first bladder wall has a gastransmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage wall thickness of 20 mils.

In an aspect, the bladder has a bladder wall having an interior-facingside and an exterior (or externally)-facing side, where the interior (orinternally)-facing side defines at least a portion of an interior regionof the bladder. The optical element having a first side and a secondopposing side can be disposed on the exterior-facing side of thebladder, the interior-facing side of the bladder, or both. As describedherein, the optical element can include the first stack and the secondstack, where the reflective layer (e.g., intermediate reflective layer)is between the first and second stack. Each of the first stack and thesecond stack can comprise two or more constituent layers. The opticalelement disposed on the exterior-facing side can have the following“in-line” configuration: exterior-facing side/first stack/reflectivelayer/second stack. The optical element disposed on the interior-facingside can have the following “in-line” configuration: firststack/reflective layer/second stack/interior-facing side. Where theoptical element is disposed on its side, the optical element is disposedon the interior-facing side or the exterior-facing side on it sideconfiguration as opposed to in line configuration.

The exterior-facing side of the bladder, the interior-facing side of thebladder, or both can optionally include a plurality of topographicalstructures (or profile features) extending from the exterior-facing sideof the bladder wall, the interior-facing side of the bladder, or both,where the first side or the second side of the optical element isdisposed on the exterior-facing side of the bladder wall and coveringthe plurality of topographical structures, the interior-facing side ofthe bladder wall and covering the plurality of topographical structures,or both, and wherein the optical element imparts a structural color tothe bladder wall.

In a particular aspect, the bladder can include a top wall operablysecured to the footwear upper, a bottom wall opposite the top wall, andone or more sidewalls extending between the top wall and the bottom wallof the inflated bladder. The top wall, the bottom wall, and the one ormore sidewalls collectively define an interior region of the inflatedbladder, and wherein the one or more sidewalls each comprise anexterior-facing side. The optical element having a first side and asecond opposing side can be disposed on the exterior-facing side of thebladder, the interior-facing side of the bladder, or both. Optionally,the exterior-facing side of the bladder, the interior-facing side of thebladder, or both can include a plurality of topographical structuresextending from the exterior-facing side of the bladder wall, theinterior-facing side of the bladder, or both, where the first side orthe second side of the a single layer or multi-layer optical film isdisposed on the exterior-facing side of the bladder wall and coveringthe plurality of topographical structures, the interior-facing side ofthe bladder wall and covering the plurality of topographical structures,or both, and wherein the single layer or multi-layer optical filmimparts a structural color to the bladder wall.

An accepted method for measuring the relative permeance, permeability,and diffusion of inflated bladders is ASTM D-1434-82-V. See, e.g., U.S.Pat. No. 6,127,026, which is incorporated by reference as if fully setforth herein. According to ASTM D-1434-82-V, permeance, permeability anddiffusion are measured by the following formulae:

Permeance

(quantity of gas)/[(area)×(time)×(pressure difference)]=permeance(GTR)/(pressure difference)=cm³/m²·atm·day (i.e., 24 hours)

Permeability

[(quantity of gas)×(film thickness)][(area)×(time)×(pressuredifference)]=permeability [(GTR)×(film thickness)]/(pressuredifference)=[(cm³)(mil)]/m²·atm·day (i.e., 24 hours)

Diffusion at One Atmosphere

(quantity of gas)/[(area)×(time)]=GTR=cm³/m²·day (i.e., 24 hours)

The bladder can include a bladder wall that includes a film including atleast one polymeric layer or at least two or more polymeric layers. Eachof the polymeric layers can be about 0.1 to 40 mils in thickness.

The polymeric layer can be formed of polymer material such as athermoplastic material as described above and herein and can be thethermoplastic layer upon which the optical element can be disposed andoptionally upon which the textured layer can be disposed or thethermoplastic layer can be used to form the textured layer, and thelike. The thermoplastic material can include an elastomeric material,such as a thermoplastic elastomeric material. The thermoplasticmaterials can include thermoplastic polyurethane (TPU), such as thosedescribed above and herein. The thermoplastic materials can includepolyester-based TPU, polyether-based TPU, polycaprolactone-based TPU,polycarbonate-based TPU, polysiloxane-based TPU, or combinationsthereof. Non-limiting examples of thermoplastic material that can beused include: “PELLETHANE” 2355-85ATP and 2355-95AE (Dow ChemicalCompany of Midland, Mich., USA), “ELASTOLLAN” (BASF Corporation,Wyandotte, Mich., USA) and “ESTANE” (Lubrizol, Brecksville, Ohio, USA),all of which are either ester or ether based. Additional thermoplasticmaterial can include those described in U.S. Pat. Nos. 5,713,141;5,952,065; 6,082,025; 6,127,026; 6,013,340; 6,203,868; and 6,321,465,which are incorporated herein by reference.

The polymeric layer can be formed of one or more of the following:ethylene-vinyl alcohol copolymers (EVOH), poly(vinyl chloride),polyvinylidene polymers and copolymers (e.g., polyvinylidene chloride),polyamides (e.g., amorphous polyamides), acrylonitrile polymers (e.g.,acrylonitrile-methyl acrylate copolymers), polyurethane engineeringplastics, polymethylpentene resins, ethylene-carbon monoxide copolymers,liquid crystal polymers, polyethylene terephthalate, polyether imides,polyacrylic imides, and other polymeric materials known to haverelatively low gas transmission rates. Blends and alloys of thesematerials as well as with the TPUs described herein and optionallyincluding combinations of polyimides and crystalline polymers, are alsosuitable. For instance, blends of polyimides and liquid crystalpolymers, blends of polyamides and polyethylene terephthalate, andblends of polyamides with styrenics are suitable.

Specific examples of polymeric materials of the polymeric layer caninclude acrylonitrile copolymers such as “BAREX” resins, available fromIneos (Rolle, Switzerland); polyurethane engineering plastics such as“ISPLAST” ETPU available from Lubrizol (Brecksville, Ohio, USA);ethylene-vinyl alcohol copolymers marketed under the tradenames “EVAL”by Kuraray (Houston, Tex., USA), “SOARNOL” by Nippon Gohsei (Hull,England), and “SELAR OH” by DuPont (Wilmington, Del., USA);polyvinylidiene chloride available from S.C. Johnson (Racine, Wis., USA)under the tradename “SARAN”, and from Solvay (Brussels, Belgium) underthe tradename “IXAN”; liquid crystal polymers such as “VECTRA” fromCelanese (Irving, Tex., USA) and “XYDAR” from Solvay; “MDX6” nylon, andamorphous nylons such as “NOVAMID” X21 from Koninklijke DSM N.V(Heerlen, Netherlands), “SELAR PA” from DuPont; polyetherimides soldunder the tradename “ULTEM” by SABIC (Riyadh, Saudi Arabia); poly(vinylalcohol)s; and polymethylpentene resins available from Mitsui Chemicals(Tokyo, Japan) under the tradename “TPX”.

Each polymeric layer of the film can be formed of a thermoplasticmaterial which can include a combination of thermoplastic polymers. Inaddition to one or more thermoplastic polymers, the thermoplasticmaterial can optionally include a colorant, a filler, a processing aid,a free radical scavenger, an ultraviolet light absorber, and the like.Each polymeric layer of the film can be made of a different ofthermoplastic material including a different type of thermoplasticpolymer.

The bladder can be made by applying heat, pressure and/or vacuum to afilm. In this regard, the optical element and optionally the texturedlayer, and the like can be disposed, formed from, or the like prior to,during, and/or after these steps. The bladder (e.g., one or morepolymeric layers) can be formed using one or more polymeric materials,and forming the bladder using one or more processing techniquesincluding, for example, extrusion, blow molding, injection molding,vacuum molding, rotary molding, transfer molding, pressure forming, heatsealing, casting, low-pressure casting, spin casting, reaction injectionmolding, radio frequency (RF) welding, and the like. The bladder can bemade by co-extrusion followed by heat sealing or welding to give aninflatable bladder, which can optionally include one or more valves(e.g., one way valves) that allows the bladder to be filled with thefluid (e.g., gas).

Now having described the optical element, the optional textured surface,and methods of making the article are now described. In an aspect, themethod includes forming the first stack (e.g., constituent layers),reflective layer (e.g., intermediate reflective layer), and the secondstack (e.g., constituent layers) of the optical element. The first stack(e.g., constituent layers), reflective layer (e.g., intermediatereflective layer), and the second stack (e.g., constituent layers) canbe formed using one or more techniques described herein.

In an aspect, the method includes forming the first stack on a surfaceof an article such as a textile, film, fiber, or monofilament yarn,where the surface can optionally be the textured surface. Subsequently,the intermediate reflective layer can be formed on the first stack andthen the second stack can be formed on the intermediate reflectivelayer. Formation of each of the first stack and the second stack willinclude formation of each constituent layer and optionally thenon-intermediate layer.

The method provides for the first stack being formed on the texturedsurface. Alternatively, the textured surface can be formed in/on theconstituent layer adjacent the surface of the article, and then theremaining constituent layers are disposed thereon. As described herein,the optical element can be formed in a layer-by-layer manner, where eachconstituent layer has a different index of refraction. As each layer isformed the undulations and flat regions are altered. The combination ofthe optional textured surface (e.g., dimensions, shape, and/or spacingof the profile elements) and the layers of the optical element (e.g.,number of layers, thickness of layers, material of the layers) and theresultant undulations and planar areas impart the structural color whenexposed to visible light. The method includes optionally forming aprotective layer over the optical element to protect the opticalelement.

Another embodiment of the present disclosure includes providing thefirst stack and the textured surface on the substrate, where the firststack (e.g., the first constituent layer) can be disposed on thetextured surface. Each constituent layer of the optical element can beformed in turn, where each layer can be formed then after an appropriateamount of time, additional processing, cooling, or the like, the nextlayer of the optical element can be formed. Optionally, non-intermediatereflective layer(s) can be formed between constituent layers. Theintermediate layer can be formed on the first stack and then the secondstack can be formed in a similar manner as the first stack. Optionally,the protective layer, by itself or in combinations with one or moreother types of layers, can be formed on the last constituent layer ofthe second stack (one on the side opposite the first stack).

Measurements for visible light transmittance and visible lightreflectance were performed using a Shimadzu UV-2600 Spectrometer(Shimadzu Corporation, Japan). The spectrometer was calibrated using astandard prior to the measurements. The incident angle for allmeasurements was zero.

The visible light transmittance was the measurement of visible light (orlight energy) that was transmitted through a sample material whenvisible light within the spectral range of 300 nanometers to 800nanometers was directed through the material. The results of alltransmittance over the range of 300 nanometers to 800 nanometers wascollected and recorded. For each sample, a minimum value for the visiblelight transmittance was determined for this range.

The visible light reflectance was a measurement of the visible light (orlight energy) that was reflected by a sample material when visible lightwithin the spectral range of 300 nanometers to 800 nanometers wasdirected through the material. The results of all reflectance over therange of 300 nanometers to 800 nanometers was collected and recorded.For each sample, a minimum value for the visible light reflectance wasdetermined for this range.

It should be emphasized that the above-described aspects of the presentdisclosure are merely possible examples of implementations and are setforth only for a clear understanding of the principles of thedisclosure. Many variations and modifications may be made to theabove-described aspects of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 weight percent toabout 5 weight percent but also include individual concentrations (e.g.,1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4percent) within the indicated range. The term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

The term “providing”, such as for “providing an article” and the like,when recited in the claims, is not intended to require any particulardelivery or receipt of the provided item. Rather, the term “providing”is merely used to recite items that will be referred to in subsequentelements of the claim(s), for purposes of clarity and ease ofreadability.

Many variations and modifications may be made to the above-describedaspects. All such modifications and variations are intended to beincluded herein within the scope of this disclosure and protected by thefollowing claims.

We claim:
 1. A method, comprising: disposing an optical element on asurface of a polymeric layer of an article, wherein the polymeric layerhas a minimum percent transmittance of 30 percent, wherein the opticalelement is disposed on a surface of a polymeric layer of the article,wherein the polymeric layer has a minimum percent transmittance of 30percent, under a given illumination condition at a first observationangle of about −15 to 180 degrees, in the wavelength range of 380 to 740nanometers, wherein the optical element has a first side and a secondside opposite the first side, wherein the optical element comprises atleast one reflective layer and a plurality of constituent layers,wherein the at least one reflective layer comprises an intermediatereflective layer that is located between two constituent layers, whereinthe intermediate layer has a minimum percent reflectance, under a givenillumination condition at a first observation angle of about −15 to 180degrees of about 60 percent or more in the wavelength range of 380 to740 nanometers, a maximum percent transmittance, under the givenillumination condition at the first observation angle of about −15 to180 degrees of 30 percent or less in the wavelength range of 380 to 740nanometers, or both, wherein the optical element imparts a firststructural color to the article from the first side of the opticalelement, wherein the optical element imparts a second structural colorto the article from the second side of the article, wherein the articleis an article of footwear, an article of apparel, or an article ofsporting equipment.
 2. The method of claim 1, wherein disposing theoptical element comprises forming the optical element on a surface of acomponent, and then disposing the component with the optical element ona surface of the article
 3. The method of claim 2, wherein the componentis a film, or a textile, or a molded component.
 4. The method of any oneof the preceding clauses, wherein forming the optical element comprisesusing: physical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, pulsedlaser deposition, sputtering, chemical vapor deposition, plasma-enhancedchemical vapor deposition, low pressure chemical vapor deposition, wetchemistry techniques, or a combination thereof.
 5. The method of claim1, wherein the article comprises a fiber, a yarn, a non-woven syntheticleather.
 6. A method comprising: disposing at least two layers of aconstituent layer onto a surface of a polymeric layer of an article toform a first stack, wherein the polymeric layer has a minimum percenttransmittance of 30 percent, under a given illumination condition at afirst observation angle of about −15 to 180 degrees in the wavelengthrange of 380 to 740 nanometers; disposing an intermediate reflectivelayer onto the first stack, wherein the intermediate reflective layerhas a first side surface adjacent the first stack and a second sidesurface on the side opposite the first side surface, wherein theintermediate layer has a minimum percent reflectance, under a givenillumination condition at a first observation angle of about −15 to 180degrees of about 60 percent or more in the wavelength range of 380 to740 nanometers, a maximum percent transmittance, under the givenillumination condition at the first observation angle of about −15 to180 degrees of 30 percent or less in the wavelength range of 380 to 740nanometers, or both; and disposing at least two layers of theconstituent layer onto the second side surface of the intermediate layerto form a second stack, wherein the first stack, the intermediatereflective layer and the second stack comprise an optical element; andwherein the optical element imparts a first structural color to thearticle from a first side of the optical element, wherein the opticalelement imparts a second structural color to the article from a secondside of the article.
 7. The method of the claim 6, wherein disposing atleast two layers of the constituent layer onto the surface of thepolymeric layer of the article to form the first stack further comprisesdisposing at least one non-intermediate layer on one of the constituentlayers, wherein the non-intermediate layer is between constituentlayers.
 8. The method of the claim 7, wherein disposing at least twolayers of the constituent layer onto the surface of the polymeric layerof the article to form the second stack further comprises disposing atleast one non-intermediate layer on one of the constituent layers,wherein the non-intermediate layer is between constituent layers.
 9. Themethod of claim 8, wherein the at least one reflective layer is made ofa metal selected from the group consisting of: titanium, aluminum,silver, zirconium, chromium, magnesium, silicon, gold, platinum, and acombination thereof, wherein the intermediate reflective layer comprisesa metal selected from the group consisting of: titanium, aluminum,silver, zirconium, chromium, magnesium, silicon, gold, platinum,niobium, an oxide of any of these, and a combination thereof, whereinthe non-intermediate reflective layer comprises a metal selected fromthe group consisting of: titanium, aluminum, silver, zirconium,chromium, magnesium, silicon, gold, platinum, niobium, an oxide of anyof these, and a combination thereof, and wherein the constituent layeris made of a material selected from the group consisting of: silicondioxide, titanium dioxide, zinc sulphide, magnesium fluoride, tantalumpentoxide, and a combination thereof.
 10. The method of claim 8, whereindisposing each of the constituent layers, the intermediate reflectivelayer, the non-intermediate reflective layer, or a combination thereofcomprises using: physical vapor deposition, electron beam deposition,atomic layer deposition, molecular beam epitaxy, cathodic arcdeposition, pulsed laser deposition, sputtering, chemical vapordeposition, plasma-enhanced chemical vapor deposition, low pressurechemical vapor deposition, wet chemistry techniques, or a combinationthereof.
 11. The method of claim 6, wherein the at least one reflectivelayer further comprises a textured surface, and the textured surface andthe optical element imparts the first structural color, the secondstructural color, or both.
 12. The method of claim 11, wherein spatialorientation of the profile features is periodic.
 13. The method of claim11, wherein spatial orientation of the profile features is a semi-randompattern or a set pattern.
 14. The method of claim 11, wherein thesurface of the layers of the inorganic optical element are asubstantially three-dimensional flat planar surface or a threedimensional flat planar surface.
 15. The method of claim 6, wherein thefirst structural color, the second structural color, or both exhibits asingle hue or multiple different hues when viewed from different viewingangles at least 15 degrees apart.
 16. The method of claim 6, wherein thepolymeric layer is colorless or wherein the polymeric layer istransparent and colored.
 17. The method of claim 6, wherein the firststructural color, the second structural color, or both have a singlehue.
 18. The method of claim 6, wherein the first structural color, thesecond structural color, or both are not iridescent.
 19. The method ofclaim 6, wherein the first structural color, the second structuralcolor, or both is visible to a viewer having 20/20 visual acuity andnormal color vision from a distance of about 1 meter from the bladder.20. The method of claim 6, wherein the at least one reflective layerfurther comprises a textured surface, and the textured surface and theoptical element imparts the first structural color, the secondstructural color, or both.